CN1993389B - Acidic activator-supports and catalysts for olefin polymerization - Google Patents

Acidic activator-supports and catalysts for olefin polymerization Download PDF

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Publication number
CN1993389B
CN1993389B CN2005800259265A CN200580025926A CN1993389B CN 1993389 B CN1993389 B CN 1993389B CN 2005800259265 A CN2005800259265 A CN 2005800259265A CN 200580025926 A CN200580025926 A CN 200580025926A CN 1993389 B CN1993389 B CN 1993389B
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contact
metallocene
compound
cyclopentadienyl
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CN1993389A (en
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M·詹森
M·P·麦克丹尼尔
J·L·马丁
杨清
G·R·霍利
T·克雷恩
E·贝纳姆
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Chevron Phillips Chemical Co LLC
Chevron Phillips Chemical Co LP
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/07—Catalyst support treated by an anion, e.g. Cl-, F-, SO42-
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
    • C08F4/6491—Catalysts containing a specific non-metal or metal-free compound organic hydrocarbon
    • C08F4/6492—Catalysts containing a specific non-metal or metal-free compound organic hydrocarbon containing aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Abstract

This invention relates to the field of olefin polymerization catalyst compositions, and methods for the polymerization and copolymerization of olefins, typically using a supported catalyst composition. In one aspect, this invention encompasses precontacting a metallocene with an olefin or alkyne monomer and an organoaluminum compound, prior to contacting this mixture with the acidic activator-support.

Description

Acidic activator-the carrier and the catalyzer that are used for the improvement of olefinic polymerization
The cross reference of related application
The application has required name to be called the U.S. Patent application sequence the 10/877th of " Improved Acidic Acticator-Supports and Catalystsfor Olefin Polymerization ", the right of priority of No. 039, it is submitted on June 25th, 2004, and is all introduced in this as reference.
Technical field
The present invention relates to the method for olefin Polymerization catalyst compositions, olefinic polymerization and the field of olefin polymer.
Background technology
Comprise that the list of ethene-1-alkene (alpha-olefin) can be with catalyst composition polymerization under promotor exists usually, described catalyst composition is used titanium, zirconium, vanadium, chromium or other metal, and these metal impregnations are on various solid support materials.These catalyst compositions can be used for ethylene homo and ethene and comonomer as propylene, 1-butylene, 1-hexene or other high alpha-olefin copolymerization.Therefore, the method existence of exploitation new olefine polymerization catalyst, catalyst activation process and preparation and use catalyzer is constantly pursued, they will provide the catalytic activity of enhancing and be applicable to the macromolecular material of specific end-use.
The catalyst system of one type comprises organometallic compound, especially metallocene compound.Known, under suitable condition, water is contacted with trimethyl aluminium and form methylaluminoxane (methyl aluminoxane), and subsequently methylaluminoxane is contacted to formation metallocene polymerization catalyzer with metallocene compound.Yet, for obtaining the high polymerization activity of expectation, a large amount of methylaluminoxane are essential, thereby a large amount of expensive trimethyl aluminium is essential, to form active metallocene catalyst.These characteristics have become the business-like obstacle of metallocene catalyst system, therefore, need to and prepare on the method for this catalyzer at catalyst composition and be improved, so that the high polymerization activity of expectation to be provided.
Needed is novel catalyst composition and the method for preparing this catalyst composition, and they provide high polymerization activity, and will allow polymer property to remain in the specialized range of expectation.A method that reaches this target is the development of new polymerization process, provides and utilization has enough highly active catalyzer the method commericially feasible.
Summary of the invention
The present invention includes the method for catalyst composition, Kaolinite Preparation of Catalyst composition and use the method for this catalyst composition olefin polymerization and acetylene.In the process of research metallocene calalyst for polymerization of olefine, find, by metallocene compound is contacted to for some time with alkene or alkyne monomer in advance with the organoaluminum promotor, can obtain the metallocene catalyst compositions activity of raising, described pre-contact is before making this mixture and acidic activator-carrier contacts.
The mixture of at least one metallocene, alkene or alkyne monomer and organoaluminum cocatalyst compound, with before activator-carrier contacts, be called as " pre-contact " mixture (precontacted mixture) at it.The mixture of metallocene, monomer, organoaluminum promotor and the activator-carrier that pre-contact mixture is contacted with acidic activator-carrier and form, be called as " rear contact " mixture (postcontacted mixture).No matter the reaction of which kind of type occurs between the ingredients of a mixture, all use this nomenclature.For example, according to this description, once contact in advance organo-aluminium compound and metallocene or multiple metallocene and alkene or alkyne monomer, mix, this contacts organo-aluminium compound in advance may have and chemical expression and the structure different for the preparation of unique organo-aluminium compound of this pre-contact mixture.Therefore, according to corresponding metallocene, organo-aluminium compound, alkene or alkynes and the acidic activator-carrier for contact with other composition in the pre-contact of preparation or rear contact mixture, describe or contact or metallocene, organo-aluminium compound, alkene or the alkynes and the acidic activator-carrier that contact afterwards in advance.
Therefore, in one aspect, catalyst composition of the present invention comprises: at least one contacts metallocene in advance; At least one pre-contact organo-aluminium compound; At least one pre-contact alkene or alkynes; With contact acidic activator-carrier after at least one.
In yet another aspect, contact in advance metallocene and comprise the compound with following formula:
(X 1)(X 2)(X 3)(X 4)M 1，
M wherein 1comprise titanium, zirconium or hafnium;
(X wherein 1) comprise independently the indenyl of cyclopentadienyl, indenyl, fluorenyl, boron benzene (boratabenzene), the cyclopentadienyl replaced, replacement, the fluorenyl of replacement or the boron benzene replaced;
Wherein belonging to (X 1) the fluorenyl of indenyl, replacement of cyclopentadienyl, replacement of described replacement or combination, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative that each substituting group on the boron benzene that replaces comprises aliphatic group, aryl, cyclic group, aliphatic group and cyclic group independently, any one in these has 1 to 20 carbon atom; Halogenide; Or hydrogen;
Wherein at (X 1) at least one substituting group optionally for connecting (X 1) and (X 2) bridging group;
(X wherein 3) and (X 4) be combination, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative of aliphatic group, aryl, cyclic group, aliphatic group and cyclic group independently, any one in these has 1 to 20 carbon atom; Or halogenide;
(X wherein 2) be combination, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative of cyclopentadienyl group, indenyl group, fluorenyl groups, boron phenyl group, aliphatic group, aryl, cyclic group, aliphatic group and cyclic group independently, any one in these has 1 to 20 carbon atom; Or halogenide;
(the X wherein replaced 2) on each substituting group be combination, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative of aliphatic group, aryl, cyclic group, aliphatic group and cyclic group independently, any one in these has 1 to 20 carbon atom; Halogenide; Or hydrogen; With
Wherein at (X 2) at least one substituting group optionally for connecting (X 1) and (X 2) bridging group.
In another aspect of this invention, contact in advance organo-aluminium compound and comprise the organo-aluminium compound with following formula:
Al(X 5) n(X 6) 3-n，
(X wherein 5) be the alkyl with 2 to 20 carbon atoms; (X 6) be its any one there is alkoxide or aryl oxide (aryloxide), halogenide or the hydride of 1 to 20 carbon atom; With n be 1 to 3 number, 1 and 3 be also included within.
Still in another aspect of this invention, contact in advance alkene or alkynes and comprise that per molecule has 2 to 30 carbon atoms and has the compound of at least one carbon-to-carbon double bond or at least one carbon-to-carbon triple bond.
Another aspect of the present invention is the rear contact acidic activator-carrier comprised with the soild oxide of electrophilic anionic treatments, wherein:
Described soild oxide is silicon-dioxide, aluminum oxide, silica-alumina, aluminum phosphate, assorted poly-tungstate (heteropolytungstates), titanium dioxide, zirconium white, magnesium oxide, boron oxide, zinc oxide, their mixed oxide or their mixture; With
Described electrophilic negatively charged ion is fluorochemical, muriate, bromide, phosphoric acid salt, fluoroform sulphonate (triflate), hydrosulfate, vitriol or its any combination.
In one aspect of the invention, metallocene compound comprises for example two (indenyl) zirconium dichloride (Ind of luxuriant zirconium 2zrCl 2) or two (cyclopentadienyl) zirconium dichloride (Cp 2zrCl 2), it is used with together with the silica-alumina acidic activator-carrier of triethyl aluminum catalyst and fluoridation.Activator-carrier of the present invention, the silica-alumina of wherein fluoridizing is an example, than corresponding untreated solid oxidation compounds, shows the acidity of enhancing.Than corresponding untreated soild oxide, activator-carrier also works as catalyst activator.Therefore, acidic activator-carrier works as " activator ", and this is because it is not only the inert support composition in catalyst composition, and relates to impact observation catalytic chemistry (observedcatalytic chemistry).
In another aspect of this invention, for example, pre-contact metallocene compound and 1-hexene and triethyl aluminum at least 10 minutes usually, before this occurs in and makes this mixture for example fluorinated silica-aluminum oxide contacts with acidic activator-carrier, than using identical component but, without the catalyst composition of pre-contact procedure, the productive rate of olefinic polymerization subsequently improves several times.Increased activity catalyst composition of the present invention can be used for the equal polymerization of 'alpha '-olefin monomers, for the copolymerization of alpha-olefin and comonomer, and also for the polymerization of alkynes.
The present invention also comprises the method for Kaolinite Preparation of Catalyst composition, and the method is utilized at least one metallocene catalyst, at least one organo-aluminium compound and acidic activator-carrier as promotor.Method of the present invention comprises makes metallocene catalyst contact in advance with alkene or acetylene hydrocarbon compound with the organoaluminum promotor, this is before making this pre-contact mixture and acidic activator-carrier contacts, and described alkene or acetylene hydrocarbon compound usually but must be for not being aggregated or the monomer of copolymerization.Inter alia, these class methods allow to obtain high polymerization activity and productive rate.
Therefore, on the one hand, the invention provides the method that produces catalyst composition, comprising:
Make at least one metallocene, at least one organo-aluminium compound and at least one alkene or alkynes contact first paragraph time, with formation, comprise that at least one contacts metallocene in advance, at least one contacts the pre-contact mixture of organo-aluminium compound and at least one pre-contact alkene or alkynes in advance; With
Make this pre-contact mixture contact the second segment time with at least one acidic activator-carrier, with formation, comprise the metallocene contacted after at least one, the rear contact mixture that contacts organo-aluminium compound, at least one rear contact alkene or alkynes and at least one rear contact acidic activator-carrier after at least one.
Further, the present invention includes catalyst composition, it comprises the ring-type organo-aluminium compound, aluminium pentamethylene (aluminacyclopentane) especially, and it derives from the organoaluminum promotor and contacts with the pre-of unsaturated compound.The present invention also comprises the method for Kaolinite Preparation of Catalyst composition, and described method produces the ring-type organo-aluminium compound from pre-contact of organoaluminum promotor and unsaturated compound.
Alkene or alkynes polymerization process that the present invention further comprises the method for novel catalyst composition, Kaolinite Preparation of Catalyst composition and causes the productive rate of raising, do not need to use a large amount of additionally expensive organoaluminum promotors of concentration.
In addition, the present invention relates to be included under polymerizing condition at least one monomer of contact and catalyst composition to produce the method for polymkeric substance.Therefore, the present invention includes use as described in this article and the catalyst composition olefin polymerization of preparation and the method for alkynes.
The present invention also comprises goods, and these goods comprise the polymkeric substance of producing with catalyst composition of the present invention.
After the detailed description of the feature of the present disclosure below having read, these and other feature of the present invention, aspect, embodiment and advantage will become apparent.
The following patent application of submitting to the same period with the application intactly is incorporated herein by reference: U.S. Patent application the 10/876th, No. 930; U.S. Patent application the 10/876th, No. 891; U.S. Patent application the 10/876th, No. 948; With U.S. Patent application the 10/877th, No. 021.
The method that the invention provides the method for novel catalyst composition, Kaolinite Preparation of Catalyst composition and use this catalyst composition olefin polymerization and alkynes.On the one hand, catalyst composition of the present invention comprises: the metallocene of at least one pre-contact; The organo-aluminium compound of at least one pre-contact; Alkene or the alkynes of at least one pre-contact; And the acidic activator-carrier of contact after at least one.
Again on the other hand, the invention provides: except the organo-aluminium compound of the metallocene of contact in advance, pre-contact, the pre-alkene contacted or alkynes, with the rear acidic activator-carrier contacted, comprise the catalyst composition of optional promotor.On the one hand, this optional promotor can be at least one aikyiaiurnirsoxan beta, at least one organoboron compound, at least one ionization ionic compound or their arbitrary combination.On the other hand, this optional promotor can be used in pre-contact procedure, in rear contact procedure or in two steps.Further, the arbitrary combination of promotor can be used in arbitrary step or two steps in.
Still on the other hand, the invention provides the method that produces catalyst composition, comprise: make metallocene, organo-aluminium compound and alkene or alkynes contact first paragraph time, with formation, comprise pre-contact metallocene, the pre-contact mixture that contacts organo-aluminium compound and contact in advance alkene or ethene in advance; With make pre-contact mixture contact the second segment time with acidic activator-carrier, comprise rear contact metallocene, rear contact organo-aluminium compound, rear contact alkene or alkynes and the rear contact mixture that contacts afterwards acidic activator-carrier with formation.
Catalyst composition and composition
Metallocene compound
The invention provides the catalyst composition that comprises at least one metallocene compound, at least one organo-aluminium compound, at least one alkene or alkynes and at least one acidic activator-carrier.On the one hand, make metallocene compound contact to form pre-contact mixture with organo-aluminium compound in advance with alkene or alkynes, this is before making this pre-contact mixture and acidic activator-carrier contacts.Metallocene compound can comprise the metallocene compound of titanium, zirconium and hafnium.
On the one hand, metallocene compound is used to prepare pre-contact mixture, and metallocene compound (metallocene compound) comprises the compound with following formula:
(X 1) (X 2) (X 3) (X 4) M 1, wherein
M wherein 1titanium, zirconium or hafnium;
(X wherein 1) be the cyclopentadienyl of cyclopentadienyl, indenyl, fluorenyl, boron benzene, replacement, the indenyl of replacement, the fluorenyl of replacement or the boron benzene replaced independently;
Wherein be positioned at (X 1) in the fluorenyl of indenyl, replacement of cyclopentadienyl, replacement of described replacement or each substituting group on the boron benzene that replaces be independently: the combination of aliphatic group, aryl, cyclic group, aliphatic group and cyclic group, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative, any one in them has 1 to 20 carbon atom; Halogenide; Or hydrogen;
Wherein at (X 1) at least one substituting group optionally for connecting (X 1) and (X 2) bridging group;
(X wherein 3) and (X 4) be independently combination, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative of aliphatic group, aryl, cyclic group, aliphatic group and cyclic group, any one in them has 1 to 20 carbon atom; Or halogenide;
(X wherein 2) be independently combination, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative of cyclopentadienyl group, indenyl group, fluorenyl groups, boron phenyl group, aliphatic group, aryl, cyclic group, aliphatic group and cyclic group, any one in them has 1 to 20 carbon atom; Or halogenide;
(the X wherein replaced 2) on each substituting group be independently combination, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative of aliphatic group, aryl, cyclic group, aliphatic group and cyclic group, any one in them has 1 to 20 carbon atom; Halogenide; Or hydrogen; With
Wherein at (X 2) at least one substituting group optionally for connecting (X 1) and (X 2) bridging group.
On the one hand, following group can be elected to be (X independently 1) and (X 2) on substituting group, or can be elected to be independently (X 2), (X 3) or (X 4) part itself: the combination of aliphatic group, aryl, cyclic group, aliphatic group and cyclic group, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or its substitutive derivative, any one in them has 1 to 20 carbon atom; Or halogenide; As long as these groups do not stop the activity of catalyst composition.This inventory comprises the substituting group characterized more than by these kinds, for example benzyl.Further, hydrogen can be selected as (X 1) and (X 2) on substituting group, as long as these groups do not stop the activity of catalyst composition, the concept of the indenyl therefore replaced and the fluorenyl of replacement comprises and indenyl and the fluorenyl of fractional saturation includes but not limited to tetrahydro indenyl, tetrahydrofluorenyl and octahydrofluorenyl.
The example of each of these groups includes but not limited to following group.In each example be described below, unless otherwise indicated, R is independently: aliphatic group; Aryl; Cyclic group; Or their arbitrary combination; Or their any substitutive derivative, include but not limited to their halogenide-, alkoxide-(alkoxide-) or acid amides-substitutive derivative; Any one in them has 1 to 20 carbon atom; Or hydrogen.Unsubstituted, the side chain arbitrarily or the straight chain analogue that also comprise them in these groups.
In each situation, the example of aliphatic group (aliphatic groups) includes but not limited to alkyl group, group of naphthene base, kiki alkenyl group, cycloalkenyl groups, alkynyl group, alkadienyl group, cyclic aliphatic group and similar group, and comprise they all replacements, unsubstituted, side chain and straight chain analogue or derivative, all there is 1 to 20 carbon atom in each situation.Therefore, aliphatic group includes but not limited to alkyl for example paraffins and alkenyl.For example, aliphatic group used herein comprises methyl, ethyl, propyl group, normal-butyl, the tertiary butyl, sec-butyl, isobutyl-, amyl group, isopentyl, hexyl, cyclohexyl, heptyl, octyl group, nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl and similar group.
In each situation, the example of aromatic yl group (aromatic groups) includes but not limited to phenyl, naphthyl, anthryl (anthacenyl) and analogue, the substitutive derivative that comprises them, in each situation, it has 6 to 25 carbon atoms.The substitutive derivative of aromatic compound includes but not limited to tolyl, xylyl, mesityl (mesityl) and analogue, comprises their any heteroatoms substitutive derivative.
In each situation, the example of cyclic group (cyclic groups) includes but not limited to that cycloalkanes, cyclenes, cycloalkyne (cycloalkynes), aryl are as phenyl, bicyclic radicals and analogue, the substitutive derivative that comprises them, in each situation, it has 3 to 20 carbon atoms.Therefore, the cyclic group that heteroatoms replaces is included at this as furyl.Cyclic hydrocarbon group group for example aryl, cycloalkyl, cycloalkenyl group, cycloalkadienyl, aralkyl, arylalkenyl, sweet-smelling alkynyl and similar group also is included.
In each situation, aliphatic cyclic group (aliphatic and cyclic groups) is the group with aliphatic series part and circular part, and its example includes, but are not limited to group as-(CH 2) mc 6h qr 5-q, wherein m is from 1 to 10 integer, and q is from 1 to 5 integer, and 1 and 10 and 1 and 5 are included;-(CH 2) mc 6h qr 10-q, wherein m is 1 to 10 integer, and q is 1 to 10 integer, and 1 and 10 are all included; With-(CH 2) mc 5h qr 9-q, wherein m is from 1 to 10 integer, and q is from 1 to 9 integer, and 1 and 10 and 1 and 9 are included.In each case and as defined above, R is independently: aliphatic group; Aryl; Cyclic group; Their any combination; Their any substitutive derivative, include but not limited to its halogenide-, alkoxide-or derivative of replacing of acid amides; Any one in them has 1 to 20 carbon atom; Or hydrogen.In one aspect, aliphatic cyclic group includes but not limited to :-CH 2c 6h 5;-CH 2c 6h 4f;-CH 2c 6h 4cl;-CH 2c 6h 4br;-CH 2c 6h 4i;-CH 2c 6h 4oMe;-CH 2c 6h 4oEt;-CH 2c 6h 4nH 2;-CH 2c 6h 4nMe 2;-CH 2c 6h 4nEt 2;-CH 2cH 2c 6h 5;-CH 2cH 2c 6h 4f;-CH 2cH 2c 6h 4cl;-CH 2cH 2c 6h 4br;-CH 2cH 2c 6h 4i;-CH 2cH 2c 6h 4oMe;-CH 2cH 2c 6h 4oEt;-CH 2cH 2c 6h 4nH 2; CH 2cH 2c 6h 4nMe 2;-CH 2cH 2c 6h 4nEt 2; Their any positional isomers (regioisomer), and the derivative of their any replacement.
In each situation, the example of halogenide (halides) comprises fluorochemical, muriate, bromide and iodide.
In each situation, oxygen groups (oxygen groups) is oxy radical (oxygen-containing groups), its example include but not limited to alkoxyl group or aryloxy group (OR) ,-OC (O) R ,-OC (O) H ,-OSiR 3,-OPR 2,-OAlR 2reach analogue, comprise their substitutive derivative, wherein R is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl or substituted aralkyl in each situation, and they have 1 to 20 carbon atom.The example of alkoxyl group or aryloxy (OR) group includes, but are not limited to methoxyl group, oxyethyl group, phenoxy group, butoxy, phenoxy group, substituent phenoxy and analogue.
In each situation, methylthio group (sulfur groups) is sulfur-containing group (sulfur-containinggroups), include, but are not limited to-SR of its example ,-OSO 2r ,-OSO 2oR ,-SCN ,-SO 2r and analogue, comprise their substitutive derivative, and wherein R is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl or substituted aralkyl in each situation, and they have 1 to 20 carbon atom.
In each situation, nitrogen groups (nitrogen groups) is nitrogen-containing group (nitrogen-containing groups), its include but not limited to-NH 2,-NHR ,-NR 2,-NO 2,-N 3reach analogue, comprise their substitutive derivative, wherein R is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl or substituted aralkyl in each situation, and they have 1 to 20 carbon atom.
In each situation, phosphorus group (phosphorus groups) is phosphorus-containing groups (phosphorus-containing groups), its include but not limited to-PH 2,-PHR ,-PR 2,-P (O) R 2, ,-P (OR) 2,-P (O) (OR) 2reach analogue, comprise their substitutive derivative, wherein R is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl or substituted aralkyl in each situation, and they have 1 to 20 carbon atom.
In each situation, arsyl group (arsenic groups) is arsenic-containing group (arsenic-containing groups), its include but not limited to-AsHR ,-AsR 2,-As (O) R 2,-As (OR) 2,-As (O) (OR) 2reach analogue, comprise their substitutive derivative, wherein R is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl or substituted aralkyl in each situation, and they have 1 to 20 carbon atom.
In each situation, carbon-based group (carbon groups) is carbon-containing group (carbon-containing groups), it includes but not limited to the alkylogen group, it comprises the alkyl group with 1 to 20 carbon atom that halogenide replaces, aromatic alkyl group with 1 to 20 carbon atom,-C (O) H,-C (O) R,-C (O) OR, cyano group,-C (NR) H,-C (NR) R,-C (NR) OR and analogue, the substitutive derivative that comprises them, wherein R is alkyl in each situation, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl or substituted aralkyl, they have 1 to 20 carbon atom.
In each situation, silicon group (silicon groups) is silicon-containing group (silicon-containinggroups), it includes but not limited to silyl-group, for example alkyl silyl-group, aryl silyl-group, aralkyl silyl-group, siloxy groups and analogue, it has 1 to 20 carbon atom in each situation.For example, silicon group comprises trimethyl silyl and phenyl octyl group silyl-group.
In each situation, germanium group (germanium groups) is germanic group (germanium-containing groups), it includes but not limited to germyl, for example alkyl germyl group, aryl germyl group, arylalkyl germyl group, first germanium alkoxy base (germyloxygroups) and analogue, it has 1 to 20 carbon atom in each situation.
In each situation, tin group (tin groups) is containing tin group (tin-containinggroups), it includes but not limited to stannyl, for example alkyl stannyl group, aryl stannyl group, arylalkyl stannyl group, first tin alkoxy base (stannoxy groups) (or " first tin alkoxyl group (stannyloxy) ") and analogue, it has 1 to 20 carbon atom in each situation.Therefore, tin group includes but not limited to first tin alkoxy base.
In each situation, lead base group (lead groups) is leaded group (lead-containinggroups), it includes but not limited to lead alkylide group, leadarylide group, arylalkyl lead base group and analogue, and it has 1 to 20 carbon atom in each situation.
In each situation, boron group (boron groups) is boron-containing group (boron-containinggroups), its include but not limited to-BR 2,-BX 2,-BRX, wherein X is the single anion group, for example halogenide, hydride, alkoxide, alkyl sulfide alcohol ester (alkyl thiolate) and analogue, wherein R is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl or substituted aralkyl in each situation, and they have 1 to 20 carbon atom.
In each situation, aluminium base group (aluminum groups) is the group (aluminum-containing groups) containing aluminium, its include but not limited to-AlR 2,-AlX 2,-AlRX, wherein X is the single anion group, for example halogenide, hydride, alkoxide, alkyl sulfide alcohol ester and analogue, and wherein R is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl or substituted aralkyl in each situation, they have 1 to 20 carbon atom.
In each situation, can be used as the include but not limited to-SO of example of the substituent inorganic group (inorganic groups) of substituted cyclopentadienyl, substituted indenyl, replacement fluorenyl and replacement boron benzene 2x ,-OAlX 2,-OSiX 3,-OPX 2,-SX ,-OSO 2x ,-AsX 2,-As (O) X 2,-PX 2and analogue, wherein X is the single anion group, for example halogenide, hydride, acid amides, alkoxide, alkyl sulfide alcohol ester and analogue, and wherein any alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl or the substituted aralkyl on these parts or substituting group have 1 to 20 carbon atom.
In each situation, the example that can be used as the substituent organometallic group (organometallic groups) of substituted cyclopentadienyl, substituted indenyl and replacement fluorenyl comprises, but be not limited to organic boron group, organoaluminum group, Organogallium group, organosilicon radical, organic germanium group, organotin group, organic lead base group, organic transition metal group and analogue, it has 1 to 20 carbon atom.
In one aspect of the invention, (X 3) and (X 4) be halogenide or the alkyl with 1 to 10 carbon atom.More typically, (X 3) and (X 4) be fluorine, chlorine or methyl.
On the other hand, due to (X 1) and (X 2) may select, metallocene of the present invention can comprise monocycle (cyclopentadienyl) compound (monokis (cyclopenta-dienyl) compound), two (cyclopentadienyl) compound, monocycle (indenyl) compound, two (indenyl) compound, monocycle (fluorenyl) compound, two (fluorenyl) compound, (cyclopentadienyl) (indenyl) compound, (cyclopentadienyl)-(fluorenyl) compound, (indenyl) (fluorenyl) compound, their replacement analogue, their bridging analogue and analogue.Therefore, at (X 2) at least one substituting group optionally for connecting (X 1) and (X 2) bridging group.
In one aspect of the invention, (X 1) be independently cyclopentadienyl, indenyl, fluorenyl, boron benzene, substituted cyclopentadienyl, substituted indenyl, replacement fluorenyl, replace boron benzene; (X 2) be independently combination, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative of cyclopentadienyl group, indenyl group, fluorenyl groups, boron phenyl group, aliphatic group, aromatic group, cyclic group, aliphatic group and cyclic group, any one in them has 1 to 20 carbon atom; Or halogenide; As long as these groups do not stop the activity of catalyst composition.
At (X 1) or (X 2) at least one substituting group can be optionally to connect or bridging (X 1) and (X 2) bridging group of part, as long as these bridging groups do not stop the activity of catalyst composition.Connect (X 1) and (X 2) key, i.e. the shortest connection of bridging part, can be the single atom that is selected from carbon, silicon, germanium or tin atom.In one aspect, bridge formation atom is carbon or Siliciumatom, and in this case, bridge comprises methylene radical (or methylene radical (the methylidene)) group of replacement or the silylene group of replacement.On the other hand, connect (X 1) and (X 2) key, i.e. the shortest connection of bridging part, can be 2 to 4 atoms.Still on the other hand, connect (X 1) and (X 2) key, i.e. the shortest connection of bridging part, can comprise 2 to 4 carbon atoms.
On the other hand, the example of bridging group includes but not limited to combination, phosphorus group, nitrogen groups, organometallic group, silicon, phosphorus, boron, germanium and the analogue of aliphatic group, cyclic group, aliphatic group and cyclic group.Can be used as (X 1) and (X 2) between the example of aliphatic group of bridge include but not limited to alkyl, for example paraffins and alkene.Can be used as (X 1) and (X 2) between the example of cyclic group of bridge include but not limited to naphthenic hydrocarbon, cycloolefin, cycloalkyne, aromatic hydrocarbons and analogue.Can be used as (X 1) and (X 2) between the example of organometallic group of bridge include but not limited to replace the silyl derivative, replace tin group, replace the germanium group, replace boron group and analogue.
On the other hand, optional bridging group can be replaced by least one substituting group, wherein said substituting group is independently combination, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative of aliphatic group, aryl, cyclic group, aliphatic group and cyclic group, and any one in them has 1 to 20 carbon atom; Halogenide; Or hydrogen.
Preparation can be used in organometallic compound in the present invention especially a lot of methods of metallocene reported.For example United States Patent (USP) the 4th, and 939,217,5,210,352,5,436,305,5,401,817,5,631,335,5,571,880,5,191,132,5,399,636,5,565,592,5,347,026,5,594,078,5,498,581,5,496,781,5,563,284,5,554,795,5,420,320,5,451,649,5,541,272,5,705,578,5,631,203,5,654,454,5,705,579 and 5,668, No. 230 this class methods have been described, they each at this, all be incorporated herein by reference.Other method that preparation can be used in the metallocene in the present invention has been reported in following reference, such as: K ppl, A.Alt, H.G.J.Mol.Catal A.2001,165,23; Kajigaeshi, S.; Kadowaki, T.; Nishida, A.; Fujisaki, S.The Chemical Society ofJapan, 1986,59,97; Alt, H.G.; Jung, M.; Kehr, G.J.Organomet.Chem.1998,562,153-181; And Alt, H.G.; Jung, M.J.Organomet.Chem.1998,568,87-112; They each at this, all be incorporated herein by reference.Further, the other method that preparation can metallocene compound used in this invention also is reported in Journal of Organometallic Chemistry, 1996,522,39-54, and it all is incorporated herein by reference.Following paper has also been described these class methods: Wailes, P.C.; Coutts, R.S.P.; Weigold, H.in Organometallic Chemistry of Titanium, Zironium, and Hafnium, Academic; New York, 1974.; Cardin, D.J.; Lappert, M.F.; And Raston, C.L.; Chemistry of Organo-Zirconium and-Hafnium Cormpounds; Halstead Press; New York, 1986, they each at this, all be incorporated herein by reference.
In one aspect of the invention, metallocene compound of the present invention includes, but are not limited to following compound:
Two (cyclopentadienyl) hafnium dichloride,
Two (cyclopentadienyl) zirconium dichloride,
Figure A20058002592600192
Two (the η of 1,2-second, two bases 5-1-indenyl) two n-butoxy hafnium (1,2-ethanediylbis (η 5-1-indenyl) di-n-butoxyhafnium),
Figure A20058002592600201
Two (the η of 1,2-second, two bases 5-1-indenyl) zirconium dimethyl,
Figure A20058002592600202
Two (the η of 3,3-, penta 2 bases 5-4,5,6,7-tetrahydrochysene-1-indenyl) hafnium dichloride,
Two (the η of aminomethyl phenyl silyl 5-4,5,6,7-tetrahydrochysene-1-indenyl) zirconium dichloride,
Two (n-butyl cyclopentadienyl) two (tertiary fourth amino) hafnium,
Figure A20058002592600205
Two (1-normal-butyl-3-methyl-cyclopentadienyl) zirconium dichloride,
Figure A20058002592600211
Two (n-butyl cyclopentadienyl) zirconium dichloride,
Figure A20058002592600212
Two (1-indenyl) zirconium dichlorides of dimetylsilyl,
Figure A20058002592600213
Two (1-indenyl) hafnium dichloride of octyl group (phenyl) silyl,
Figure A20058002592600214
Two (the η of dimetylsilyl 5-4,5,6,7-tetrahydrochysene-1-indenyl) zirconium dichloride,
Two (2-methyl isophthalic acid-indenyl) zirconium dichlorides of dimetylsilyl,
Figure A20058002592600221
Two (9-fluorenyl) zirconium dichlorides of 1,2-second, two bases,
Figure A20058002592600222
Indenyl diethoxy titanium chloride (IV),
Figure A20058002592600223
(isopropylamino dimetylsilyl) CyclopentadienyltitaDichloride Dichloride,
Figure A20058002592600224
Two (pentamethyl-cyclopentadienyl) zirconium dichloride,
Two (indenyl) zirconium dichloride,
Figure DEST_PATH_GSB00000151587900031
Two (9-fluorenyl) zirconium dichlorides of methyl (octyl group) silyl,
Two (2,7-di-t-butyl fluorenyl)-ethyl-1,2-bis-base zirconium dichlorides (IV),
Two-[1-(N, N-diisopropylaminoethyl) boron benzene] hydrogenation trifluoromethane sulfonic acid zirconium,
Methyl-3-butenyl methylene radical (η 5-cyclopentadienyl) (η 5-9-fluorenyl) zirconium dichloride, [(η 5-C 5h 4) CCH 3(CH 2cH 2cH=CH 2) (η 5-9-C 13h 9)] ZrCl 2;
Methyl-3-butenyl methylene radical (η 5-cyclopentadienyl) (η 5-2,7-bis--tertiary butyl-9-fluorenyl) zirconium dichloride, [(η 5-C 5h 4) CCH 3(CH 2cH 2cH=CH 2) (η 5-9-C 13h 7-2,7- tbu 2)] ZrCl 2;
Methyl-4-pentenyl methylene radical (η 5-cyclopentadienyl) (η 5-9-fluorenyl) zirconium dichloride, [(η 5-C 5h 4) CCH 3(CH 2cH 2cH 2cH=CH 2) (η 5-9-C 13h 9)] ZrCl2;
Methyl-4-pentenyl methylene radical (η 5-cyclopentadienyl) (η 5-2,7-bis--tertiary butyl-9-fluorenyl) zirconium dichloride, [(η 5-C 5h 4) CCH 3(CH 2cH 2cH 2cH=CH 2) (η 5-9-C 13h 7-2,7- tbu 2)] ZrCl 2;
Phenyl-3-butenyl methylene radical (η 5-cyclopentadienyl) (η 5-9-fluorenyl) zirconium dichloride, [(η 5-C 5h 4) C (C 6h 5) (CH 2cH 2cH=CH 2) (η 5-9-C 13h 9)] ZrCl 2;
Phenyl-3-butenyl methylene radical (η 5-cyclopentadienyl) (η 5-2,7-bis--tertiary butyl-9-fluorenyl) zirconium dichloride, [(η 5-C 5h 4) C (C 6h 5) (CH 2cH 2cH=CH 2) (η 5-9-C 13h 7-2,7- tbu 2)] ZrCl 2;
Phenyl-4-pentenyl methylene radical (η 5-cyclopentadienyl) (η 5-9-fluorenyl) zirconium dichloride, [(η 5-C 5h 4) C (C 6h 5) (CH 2cH 2cH 2cH=CH 2) (η 5-9-C 13h 9)] ZrCl 2;
Phenyl-4-pentenyl methylene radical (η 5-cyclopentadienyl) (η 5-2,7-bis--tertiary butyl-9-fluorenyl) zirconium dichloride, [(η 5-C 5h 4) C (C 6h 5) (CH 2cH 2cH 2cH=CH 2) (η 5-9-C 13h 7-2,7- tbu 2)] ZrCl 2; And analogue.
Still in another aspect of this invention, in catalyst composition of the present invention, the example of useful metallocene comprises the compound with formula I:
Figure A20058002592600241
Wherein E is C, Si, Ge or Sn; R1 is H or the hydrocarbyl group with 1 to 12 carbon atom; R2 is the kiki alkenyl group with 3 to 12 carbon atoms; With R3 be H or the hydrocarbyl group with 1 to 12 carbon atom.
On the other hand, catalyst composition of the present invention comprises the metallocene compound that formula II is described below:
Figure A20058002592600242
Wherein R1 is methyl or phenyl; R2 is 3-butenyl (CH 2cH 2cH=CH 2) or 4-pentenyl (CH 2cH 2cH 2cH=CH 2); With R3 be H or the tertiary butyl.
Typically, organometallic compound (organometal compound) comprises two (n-butyl cyclopentadienyl) zirconium dichlorides; Two (indenyl) zirconium dichloride; Two (1-indenyl) zirconium dichlorides of dimetylsilyl; Two (9-fluorenyl) zirconium dichlorides of Methyl Octyl silyl; Or two (2,7-, bis--tertiary butyl fluorenyl)-ethyl-1,2-bis-base zirconium dichlorides (IV).
Organo-aluminium compound (organoaluminum compound)
On the one hand, the invention provides catalyst composition, it comprises at least one metallocene compound, at least one organo-aluminium compound, at least one alkene or alkynes and at least one acidic activator-carrier.On the other hand, metallocene compound contacts to form pre-contact mixture with organo-aluminium compound in advance with alkene or alkynes, and this carried out before making this pre-contact mixture and acidic activator-carrier contacts.Typically, a part of organo-aluminium compound is added in this pre-contact mixture, and another part organo-aluminium compound is added in rear contact mixture, although all organo-aluminium compounds can be used to Kaolinite Preparation of Catalyst in pre-contact procedure.
In another aspect of this invention, except at least one metallocene and alkene or ethane monomer, pre-contact mixture can comprise the first organo-aluminium compound, and rear contact mixture can also comprise the second organo-aluminium compound except pre-contact mixture and acidic activator-carrier.The second organo-aluminium compound can be identical or different with the first organo-aluminium compound.Particularly, any the first possible organo-aluminium compound can also be used as the selection of the second organo-aluminium compound, yet, be not that all possible the second organo-aluminium compound is all worked well as the first organo-aluminium compound be used in pre-contact mixture.
Still on the other hand, can together with alkene or alkyne monomer, be used in metallocene compound in the present invention the first organo-aluminium compound in pre-contact mixture include but not limited to have below the compound of general formula:
Al(X 5) n(X 6) 3-n，
(X wherein 5) be the alkyl with 2 to 20 carbon atoms, and (X 6) be any one alkoxide or aryl oxide, halogenide or hydride with 1 to 20 carbon atom; With n be 1 to 3 number, 1 and 3 be also included within.In one aspect, (X 5) be the alkyl with 2 to 10 carbon atoms.On the other hand, (X 5) be ethyl, propyl group, normal-butyl, sec-butyl, isobutyl-, hexyl and analogue.
Substituting group (X in this formula of the first organo-aluminium compound 6) be any one alkoxide or aryl oxide, halogenide or hydride with 1 to 20 carbon atom.On the one hand, (X 6) be fluorine or chlorine independently, and on the other hand, (X 6) be chlorine.
At the formula Al of the first organo-aluminium compound (X 5) n(X 6) 3-nin, n comprises 1 and 31 to 3 number, and typically, n is 3.The value of n is not defined as integer, so this formula comprises sesquihalide (sesquihalide) compound.
Still on the other hand, can be used in rear contact mixture the compound that second organo-aluminium compound that can be used in the contacting subsequently of pre-contact composition and extra organo-aluminium compound and activator-carrier includes but not limited to have following general formula:
Al(X 5) n(X 6) 3-n，
(X wherein 5) be the alkyl with 1 to 20 carbon atom, and (X 6) be any one alkoxide or aryl oxide, halogenide or hydride with 1 to 20 carbon atom; With n be 1 to 3 number, 1 and 3 be also included within.In one aspect, (X 5) be the alkyl with 1 to 10 carbon atom, and on the other hand, (X 5) be methyl, ethyl, propyl group, normal-butyl, sec-butyl, isobutyl-, hexyl and similar group.
Substituting group (X in the formula of the second organo-aluminium compound 6) be any one alkoxide or aryl oxide, halogenide or hydride with 1 to 20 carbon atom.On the one hand, (X 6) be fluorine or chlorine independently, and on the other hand, (X 6) be chlorine.
At the second organo-aluminium compound formula Al (X 5) n(X 6) 3-nin, n comprises 1 and 31 to 3 number, and typically, n is 3.The value of n is not defined as integer, so this formula comprises the sesquihalide compound.
Generally speaking, the example that can be used in the organo-aluminium compound in the present invention includes, but are not limited to trialkyl aluminium compound, dialkyl monohalide aluminum compound (dialkylaluminium halide compounds), dihalide alkylaluminium cpd, half halogenated alkyl aluminum compound (alkylaluminium sesquihalidecompounds) and their composition.The object lesson that can be used in organometallic compound in the present invention the organo-aluminium compound in pre-contact mixture together with alkene or alkyne monomer includes but not limited to: triethyl aluminum (TEA), tri-propyl aluminum, diethyl aluminum ethylate (diethylaluminium ethoxide), tri-butyl aluminum, diisobutylaluminium hydride, triisobutyl aluminium and diethylaluminum chloride.
When pre-contact mixture comprises that the first organo-aluminium compound and rear contact mixture comprise the second organo-aluminium compound, any the first possible organo-aluminium compound can also be used as the selection of the second organo-aluminium compound.Yet, be not all possible the second organo-aluminium compound be used in pre-contact mixture all work good.For example, triethyl aluminum (TEA) is all worked good in pre-contact and rear contact mixture, yet trimethyl aluminium (TMA) is only worked well in rear contact mixture, and it is bad in pre-contact mixture, to work.In this example, can be used as the organo-aluminium compound that the second organo-aluminium compound uses in rear contact mixture and include, but are not limited to be used in all compounds in pre-contact mixture, and further comprise trimethyl aluminium (TMA).
The amount of disclosed organo-aluminium compound comprises the total amount that is used in the organo-aluminium compound in pre-contact and rear contact mixture and is added into any other organo-aluminium compound in polymerization reactor in this article.Therefore, disclose the total amount of machine aluminium compound, the organo-aluminium compound of not considering to use single organo-aluminium compound or using more than one.When only using single organo-aluminium compound, triethyl aluminum (TEA) is the typical compound in using in this aspect of the invention.
Alkene or ethane monomer
In the present invention, for active polymerizing catalyst is provided, at least one organo-aluminium compound, at least one metallocene compound and at least one alkene or alkyne monomer are contacted in advance, before this occurs in and makes this mixture and solid acid activator-carrier contacts.
In pre-contact procedure and in the polymerization process with catalyst composition of the present invention, useful unsaturated reactant comprises olefin(e) compound, and its per molecule has 2 to 30 carbon atoms, and has at least one olefinic double bonds.The present invention includes the homopolymerization process of using single alkene, and the copolymerization of the olefin(e) compound different from least one.Usually, the multipolymer of ethene comprises the comonomer (<50 molar percentage) of the ethene of main amount (>50 molar percentage) and minor amount, although this is not prerequisite.Can should there are with the comonomer of ethylene copolymerization 3 to 20 carbon atoms in their molecular chain.
Acyclic, ring-type, many rings, end (α), centre, straight chain, side chain, replacement, unsubstituted, functionalized can being used in the present invention with non-functionalized alkene.For example, can include but not limited to propylene with the typical unsaturated compound of polymerization catalyst of the present invention, 1-butylene, 2-butylene, 3-methyl-1-butene, iso-butylene, the 1-amylene, the 2-amylene, the 3-Methyl-1-pentene, 4-methyl-1-pentene, the 1-hexene, the 2-hexene, the 3-hexene, 3-ethyl-1-hexene, the 1-heptene, the 2-heptene, the 3-heptene, four kinds of positive octenes (the four normal octenes), four kinds of positive nonenes (the four normal nonenes), any two or more mixture of five kinds of positive decene (the five normal decenes) and they.Ring-type and bicyclic alkene include but not limited to cyclopentenes, tetrahydrobenzene, norbornylene, norbornadiene and analogue, also can be aggregated, as mentioned above.
Acetylene also can be aggregated according to the present invention.Acyclic, ring-type, end (α), centre, straight chain, side chain, replacement, unsubstituted, functionalized can being used in the present invention with non-functionalized alkynes.The example of the alkynes that can be aggregated includes but not limited to tolane, 2-butyne, 2-hexin, 3-hexin, 2-heptyne, 3-heptyne, 2-octyne, 3-octyne, 4-octyne and analogue.
In one aspect, when expectation during multipolymer, monomer ethylene can with the copolymerization monomer copolymerizable.In one aspect of the method, the example of comonomer includes but not limited to propylene, 1-butylene, 2-butylene, 3-methyl-1-butene, iso-butylene, 1-amylene, 2-amylene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, four kinds of positive octenes, four kinds of positive nonenes or five kinds of positive decene.In one aspect of the method, comonomer can be 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene or vinylbenzene.
In one aspect, the amount of the comonomer that take in the introducing reactor zone produced multipolymer is as 0.01 to 10 weight percent of the gross weight based on monomer and comonomer generally.In one aspect of the method, the comonomer that the amount that is incorporated into the comonomer in reactor zone is 0.01 to 5 weight percent, and in yet another aspect, the gross weight based on monomer and comonomer, be 0.1 to 4 weight percent.Alternatively, can use the amount that is enough to produce above-mentioned weight concentration in produced multipolymer.
Although do not expect to be bound by this theory, in the situation that side chain, replacement or functional olefines be used as reactant, it is believed that the steric hindrance polymerization process that can stop and/or slow down.Therefore, the mode that the side chain of desired distance carbon-carbon double bond alkene to a certain degree and/or circular part (one or more) will can may not hinder with the identical alkene substituting group in more approaching carbon-carbon double bond this reaction hinders reaction.In one aspect, at least one reactant of catalyst composition of the present invention is ethene, thus polymerization be homopolymerization or from different acyclic, ring-types, end, centre, straight chain, side chain, copolymerization replacement or unsubstituted alkene.In addition, catalyst composition of the present invention can be used in the polymerization of diolefinic compound, and described diolefinic compound includes but not limited to 1,3-butadiene, isoprene, Isosorbide-5-Nitrae-pentadiene and 1,5-hexadiene.
Solid acid activator-carrier
The invention provides catalyst composition, it comprises at least one metallocene compound, at least one organo-aluminium compound, at least one alkene or alkynes and at least one acidic activator-carrier.On the one hand, metallocene compound is contacted in advance with alkene or alkynes with organo-aluminium compound, to form pre-contact mixture, before this occurs in and makes this pre-contact mixture and acidic activator-carrier contacts.
The present invention relates to comprise the catalyst composition of acidic activator-carrier, the method for preparing the catalyst composition that comprises acidic activator-carrier and the method for using these catalyst composition olefin polymerizations and acetylene.In the present invention, metallocene compound can contact the first paragraph time with alkene or ethane monomer and organo-aluminium compound, before this occurs in and makes this mixture and acidic activator-carrier contacts.Once the pre-contact mixture of metallocene, unsaturated monomer and organo-aluminium compound is contacted with acidic activator-carrier, and said composition further comprises acidic activator-carrier, be called as " rear contact " mixture.On the one hand, contact mixture can be fed to reactor---carrying out polymerization process in this reactor---further is being allowed to keep in touch the second segment time before after this.On the other hand, rear contact mixture can at once be fed in reactor after being produced, or can directly in reactor, prepare, and after preparation initiated polymerization at once.Aspect this, the second segment time that rear contact mixture is allowed to keep in touch during it is the time of the required minimum of the rear contact mixture of preparation initiated polymerization process.
In one aspect, the present invention includes the catalyst composition comprised as the chemically treated soild oxide of acidic activator-carrier, and it generally is combined with machine aluminium compound and uses together.On the other hand, described activator-carrier comprises at least one soild oxide by least one electrophilic anionic treatments; Wherein said soild oxide is silicon-dioxide, aluminum oxide, silica-alumina, aluminum phosphate, assorted poly-tungstate (heteropolytungstates), titanium dioxide, zirconium white, magnesium oxide, boron oxide, zinc oxide, their mixed oxide or their mixture; And wherein the electrophilic negatively charged ion is fluorochemical, muriate, bromide, phosphoric acid salt, fluoroform sulphonate (triflate), hydrosulfate, vitriol or its any combination.
Activator-carrier comprises the product of contact of at least one solid oxidation compounds and at least one electrophilic negative ion source.In one aspect, this solid oxidation compounds comprises inorganic oxide.Before contact electrophilic negative ion source, do not require this solid oxidation compounds of calcining.In solid oxidation compounds and electrophilic negative ion source contact process or afterwards, product of contact also can be calcined.Aspect this, the solid oxidation compounds can be calcined or can not calcined.In another aspect, activator-carrier can comprise the solid oxidation compounds of at least one calcining and the product of contact of at least one electrophilic negative ion source.
With corresponding untreated soild oxide Compound Phase ratio, activator-carrier shows the acidity of enhancing.With corresponding untreated soild oxide, compare, activator-carrier also plays a part catalyst activator.Although do not expect to be bound by theory, it is believed that, activator-carrier can play a part ionizing solid oxidation compounds by extract wholly or in part (extract) anion ligand from metallocene.Yet, activator-carrier is activator, and no matter its ionizing metallocene whether, capture anion ligand and form ion pair, weaken the metal-ligand key in metallocene, when it contacts with activator-carrier simply with anion ligand coordination, or any other mechanism that can carry out of activation.Although activator-carrier activates metallocene under the shortage promotor, eliminate promotor nonessential from catalyst composition.With the catalyst composition that contains untreated soild oxide, compare, the mobilizing function of activator-carrier is obvious generally on the activity that strengthens catalyst composition.Yet, it is believed that, activator-carrier can play the function of activator, even in the situation that lack organo-aluminium compound, aikyiaiurnirsoxan beta, organoboron compound or ionizing ionic compound.
In one aspect, activator-carrier of the present invention comprises the combination of solid inorganic oxide material, mixed oxide material or inorganic oxide material, and it carries out chemical treatment by the electrophilic component, and optionally uses metal treatment.Therefore, soild oxide of the present invention comprise oxide material as aluminum oxide, its " mixed oxide " compound as silica-alumina with and combination and mixture.Mixed oxidization compounds with more than one metals is combined with oxygen and forms the solid oxidation compounds as silica-alumina list chemofacies, and be the present invention includes.
In one aspect of the invention, activator-carrier also comprises metal or metal ion, and it is selected from zinc, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum or their any combination.The example that also comprises the activator-carrier of metal or metal ion comprises, but be not limited to the chlorinated aluminas (zinc-impregnated chloridedalumina) of zinc dipping, the fluorided alumina (zinc-impregnated fluorided alumina) of zinc dipping, chlorodioxin SiClx-the aluminum oxide (zinc-impregnated chlorided silica-alumina) of zinc dipping, fluorinated silica-the aluminum oxide (zinc-impregnated fluorided silica-alumina) of zinc dipping, sulfated alumina (zinc-impregnated sulfated alumina) or their any combination of zinc dipping.
On the other hand, activator-carrier of the present invention comprises the soild oxide of relative high porosity, its performance lewis acidity or Bronsted acidity behavior.Described soild oxide electrophilic component---is generally electrophilic negatively charged ion or electrophilic negative ion source---and carries out chemical treatment, to form activator-carrier.Although do not expect to be bound by following statement, it is believed that, process by the electrophilic component acidity that inorganic oxide increases or improved oxide compound.Therefore, activator-carrier shows general than the Louis of untreated soild oxide or large Louis or the Bronsted acidity of Bronsted acidity.A kind of method of the acidity of quantitative chemical processing and untreated soild oxide material is the polymerization activity under acid catalyzed reaction by comparison process and untreated oxide compound.Usually, according to observations, electron-withdrawing power or the lewis acidity of activator-carrier are stronger, and its polymerization activity is stronger.
In one aspect, the chemical treatment soild oxide comprises solid inorganic oxide, solid inorganic oxide is selected from the element of periodictable 2,3,4,5,6,7,8,9,10,11,12,13,14 or 15 families containing aerobic and at least one, or is selected from the element of group of the lanthanides or actinide elements containing aerobic and at least one.(referring to: Hawley ' s Condensed Chemical Dictionary, 11 thed., John Wiley & Sons; 1 995; Cotton, F.A.; Wilkinson, G.; Murillo; C.A.; And Bochmann; M.Advanced Inorganic Chemistry, 6 thed., Wiley-Interscience, 1999.) usually, inorganic oxide is selected from the element of Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn or Zr containing aerobic and at least one.
Can be used in soild oxide material in chemical treatment soild oxide of the present invention or the suitable example of compound and include, but are not limited to Al 2o 3, B 2o 3, BeO, Bi 2o 3, CdO, Co 3o 4, Cr 2o 3, CuO, Fe 2o 3, Ga 2o 3, La 2o 3, Mn 2o 3, MoO 3, NiO, P 2o 5, Sb 2o 5, SiO 2, SnO 2, SrO, ThO 2, TiO 2, V 2o 5, WO 3, Y 2o 3, ZnO, ZrO 2and analogue, comprise their mixed oxide and their composition.The example that can be used in the mixed oxide in activator-carrier of the present invention includes, but are not limited to silica-alumina, silica-titania, silicon-dioxide-zirconium white, zeolite, a lot of clay mineral, aluminum oxide-titanium dioxide, aluminium oxide-zirconium oxide and analogue.
In one aspect of the invention, the soild oxide material is chemically treated by it being contacted with at least one electrophilic negatively charged ion carry out, and described electrophilic negatively charged ion can be derived from any electrophilic component or electrophilic negative ion source.In addition, the soild oxide material is optionally used the metal ion chemical treatment, then calcines and forms the chemically treated soild oxide of containing metal or metal impregnation.Alternatively, the soild oxide material is contacted simultaneously and is calcined with the electrophilic negative ion source.Oxide compound and electrophilic component, be generally the salt of electrophilic negatively charged ion or the method for acid contact, includes but not limited to gelation, gelation, a kind of compound are impregnated into another kind of upper and similar approach altogether.Usually, after any contact method, the contact mixture of oxide compound, electrophilic negatively charged ion and optional metals ion is calcined.
Electrophilic component for the treatment of oxide compound is to increase the Louis of soild oxide or any component of Bronsted acidity after processing.In one aspect, described electrophilic component is electrophilic negative ion source compound, and it for example can be used as the source of this negatively charged ion or the volatile organic compounds of parent derived from salt, acid or other compound.The example of electrophilic negatively charged ion and electrophilic negative ion source includes but not limited to vitriol, hydrosulfate, fluorochemical, muriate, bromide, iodide, fluorosulfuric acid salt, fluoroborate, phosphoric acid salt, fluorophosphate, trifluoroacetate, fluoroform sulphonate, fluozirconate, fluotitanate, trifluoroacetate, fluoroform sulphonate and analogue, comprises their mixture and composition.In addition, other ion or the non-ionic compound as the source of these electrophilic negatively charged ion also can be used in the present invention.
When the electrophilic component comprises the salt of electrophilic negatively charged ion, the counter ion of this salt or positively charged ion can be any positively charged ions, and it makes salt reply in calcination process or decompose and reverts to acid.Indicate the factor of the suitability of the concrete salt that can be used as electrophilic negatively charged ion source to comprise, but be not limited to the ion pairing effect between shortage, positively charged ion and the negatively charged ion of the salt solubleness in solvent, positively charged ion adverse effect in expectation, hygroscopic nature and the similar factor of being given salt by positively charged ion, and the thermostability of negatively charged ion.Suitable cationic example in the salt of electrophilic negatively charged ion includes but not limited to ammonium, trialkyl ammonium, tetra-allkylammonium, tetraalkyl
Figure 10003_1
, H +, [H (OEt 2) 2] +and analogue.
Further, one or more different electrophilic negatively charged ion combinations in varing proportions can be used to make the concrete acidity of activator-carrier to be suitable for the level of expecting.The combination that can make the electrophilic component and oxide material, contact with any order of activator-support acidity so that expectation to be provided simultaneously or contact individually.For example, one aspect of the present invention is to use two or more electrophilic negative ion source compounds in the contact procedure independent at two or more.Therefore, an example of this quadrat method for preparing activator-carrier is as follows: the solid oxidation compounds selected or the combination of oxide compound are contacted with the first electrophilic negative ion source compound, to form the first mixture, then calcine this first mixture, then make the first mixture of this calcining contact with the second electrophilic negative ion source compound, to form the second mixture, calcine afterwards described the second mixture, with the solid oxidation compounds of formation processing.In such process, described the first and second electrophilic negative ion source compounds are generally different compounds, although they can be identical compounds.
In one aspect of the invention, soild oxide activator-carrier produces by following method, comprising:
1) the solid oxidation compounds contacted with at least one electrophilic negative ion source compound and form the first mixture; With
2) calcine described the first mixture and form soild oxide activator-carrier.
In another aspect of this invention, soild oxide activator-carrier produces by following method, comprising:
1) at least one solid oxidation compounds contacted with the first electrophilic negative ion source compound and form the first mixture; With
2) calcine described the first mixture and produce the first mixture of calcining;
3) make the first mixture of described calcining contact with the second electrophilic negative ion source compound and form the second mixture; With
4) calcine described the second mixture and form soild oxide activator-carrier.Therefore, described soild oxide activator-carrier is called as soild oxide or the chemically treated soild oxide of processing sometimes simply.
Another aspect of the present invention is by making at least one soild oxide contact and produce or form soild oxide activator-carrier with at least one electrophilic negative ion source compound, wherein said at least one solid oxidation compounds before contact electrophilic negative ion source, during or calcined afterwards, and wherein substantially do not have aikyiaiurnirsoxan beta and organoboron compound.
In one aspect of the invention, once soild oxide is processed and dry, it can be calcined subsequently.The calcining of the soild oxide of processing is generally under ambiance, and the typical case carries out under dry ambiance, and temperature is 200 ° to 900 ℃, and the time of carrying out 1 minute to 100 hours.In another aspect, calcining is to carry out at the temperature of 300 ℃ to 800 ℃, and in another aspect, calcining is to carry out at the temperature of 400 ℃ to 700 ℃.In a further aspect, calcining has been carried out 1 hour to 50 hours, and calcining has been carried out 3 hours to 20 hours in another aspect.In a further aspect, calcining is carried out 1 to 10 hour at the temperature of 350 ℃ to 550 ℃.
In addition, during calcining, can use the suitable environment of any type.Generally speaking, calcining is carried out under oxidizing atmosphere, for example air.Alternatively, can use inert atmosphere, for example nitrogen or argon, or reducing atmosphere, for example hydrogen or carbon monoxide.
In another aspect of this invention, for the preparation of the soild oxide component of chemical treatment soild oxide, there is the pore volume more than 0.01cc/g.In another aspect, described soild oxide component has the above pore volume of 0.1cc/g, and in a further aspect, more than 1.0cc/g.In a further aspect, described soild oxide component has 1 to 1000m 2the surface-area of/g.In another aspect, the soild oxide component has from 100 to 800m 2the surface-area of/g, and in a further aspect, from 250 to 600m 2/ g.
The soild oxide material can be processed with the combination of halide ions or sulfate ion source or negatively charged ion, and optionally with metal ion, processes, and then calcines to provide the activator-carrier of particulate solid form.In one aspect, the soild oxide material is with the source of vitriol, and---source that is called as sulfating agent (sulfating agent), chloride ion---source that is called as chlorizating agent (chloriding agent), fluoride ion---is called as fluorizating agent (fluoriding agent) or their combination and processed, and calcining is to provide the soild oxide activator.In another aspect, useful acidic activator-carrier includes but not limited to: the bromination aluminum oxide; Chlorinated aluminas; Fluorided alumina; Sulfated alumina; The aluminum oxide that hydrosulfate is processed; The bromination silica-alumina; Chlorodioxin SiClx-aluminum oxide; Fluorinated silica-aluminum oxide; The sulfation silica-alumina; Bromination silicon-dioxide-zirconium white; Chlorodioxin SiClx-zirconium white; Fluorinated silica-zirconium white; Fluorinated silica-titanium dioxide; Fluoridize-chlorinated aluminas; Sulfation silicon-dioxide-zirconium white; The chlorination Zinc aluminate; Chlorination aluminic acid tungsten; Fluorinated silica-boron oxide; The silicon-dioxide that fluoroborate is processed; Column clay (pillared clay), for example the column montmorillonite, optionally process with fluorochemical, muriate or vitriol; Phosphorylation aluminum oxide or other aluminate or phosphate (aluminophosphates), optionally use vitriol, fluorochemical or chloride treatment; Perhaps their any combination.In addition, any activator-carrier can optionally be used metal ion treatment.
In one aspect of the invention, the oxide compound activator-carrier of processing comprises the fluorinated solid oxide compound of particulate solid form, and therefore by being processed with fluorizating agent, fluoride ion source is added in oxide compound.In a further aspect, by form the slurries of oxide compound in suitable solvent, fluoride ion can be added in oxide compound, described solvent is alcohol or water for example, includes but not limited to the alcohol of 1 to 3 carbon atom, because they have volatility and low surface tension.The example that can be used in the fluorizating agent in the present invention includes, but are not limited to hydrofluoric acid (HF), Neutral ammonium fluoride (NH 4f), ammonium bifluoride (NH 4hF 2), ammonium tetrafluoroborate (ammoniumtetrafluoroborate) (NH 4bF 4), ammonium silicofluoride (ammonium silicofluoride) (hexafluorosilicate (hexafluorosilicate)) ((NH 4) 2siF 6), ammonium hexafluorophosphate (ammonium hexafluorophosphate) (NH 4pF 6), its analogue and composition thereof.For example, ammonium bifluoride NH 4hF 2can be used as fluorizating agent, reason is that it is easy to use and easily obtains.
In another aspect of this invention, soild oxide can be processed with fluorizating agent during calcining step.Can use any fluorizating agent that can fully contact soild oxide during calcining step.For example, except foregoing those fluorizating agents, can use volatility organic fluorine agent.In this aspect of the present invention, the example of useful volatility organic fluorine agent includes but not limited to freonll-11, perflexane (perfluorohexane), perfluor benzene (perfluorobenzene), methyl fuoride, trifluoroethanol and their combination.When soild oxide is fluorinated during calcining, also can use gaseous hydrogen fluoride or fluorine itself.A kind of method easily that soild oxide is contacted with fluorizating agent is during calcining, to make fluorizating agent be evaporated to the air-flow for the fluidized solids oxidation thing.
Equally, in another aspect of this invention in, chemically treated soild oxide comprises the chlorination soild oxide of particulate solid form, therefore, by being processed with chlorizating agent, the chloride ion source is added in oxide compound.By form the slurries of oxide compound in suitable solvent, chloride ion can be added in oxide compound.In another aspect of this invention, soild oxide can be processed with chlorizating agent during calcining step.During calcining step can as muriate source and fully any chlorizating agent of catalytic oxidation thing can be used.For example, can use volatility organochlorine agent.In this aspect of the present invention, the example of useful volatility organochlorine agent includes but not limited to some freonll-11, perna (perchloro benzene), methyl chloride, methylene dichloride, chloroform, tetracol phenixin, ethapon or their any composition.During calcining, itself also can be used gaseous hydrogen chloride or chlorine together with soild oxide.A kind of method easily that oxide compound is contacted with chlorizating agent is during calcining, to make chlorizating agent be evaporated to the air-flow for the fluidized solids oxidation thing.
In one aspect, the fluorochemical existed before the calcining solid oxide compound or the amount of chloride ion are generally by weight from 2 to 50%, and wherein wt per-cent is based on soild oxide before the calcining weight as silica-alumina.In another aspect, the fluorochemical existed before the calcining solid oxide compound or the amount of chloride ion are 3 to 25% by weight, and in another aspect, are 4 to 20% by weight.If fluorochemical or chloride ion are added in calcination process, for example work as at CCl 4while having lower calcining, before calcining, generally there is no fluorochemical or chloride ion in soild oxide.Once flood with halogenide, the halogenation oxide compound can come dry by any currently known methods in this area, include but not limited to that air exhaust filtering (suctionfiltration) evaporates afterwards, dry under vacuum, spraying drying and similar approach, although the soild oxide of moist dipping and to start at once calcining step be also possible.
Silica-alumina for the preparation of the silica-alumina of processing can have the pore volume more than 0.5cc/g.In one aspect, pore volume can be more than 0.8cc/g, and in another aspect, pore volume can be more than 1.0cc/g.In addition, silica-alumina can have 100m 2the surface-area that/g is above.In one aspect, surface-area is 250m 2more than/g, and in another aspect, surface-area can be 350m 2more than/g.Generally speaking, silica-alumina of the present invention has from 5 to 95% alumina content.In one aspect, the alumina content of silica-alumina can from 5 to 50%, and in another aspect, the alumina content of silica-alumina can be by weight from 8% to 30%.
Sulfated soild oxide comprises vitriol and soild oxide component for example aluminum oxide or silica-alumina, is the form of granular solids.Optionally, the sulfation oxide compound is further used metal ion treatment, so that the sulfation oxide compound of calcining contains metal.In one aspect, the sulfation soild oxide comprises vitriol and aluminum oxide.In one aspect of the invention, sulfated alumina is to form by the method that wherein aluminum oxide is processed by sulfate source, described sulfate source such as but not limited to sulfuric acid or vitriol such as ammonium sulfate.In one aspect, by the solvent suitable, for example form the slurries of aluminum oxide in alcohol or water, can carry out this process, in described solvent, the sulfating agent (sulfating agent) of expectation concentration is added into.Suitable organic solvent includes, but are not limited to the alcohol of 1 to 3 carbon atom, and reason is their volatility and low surface tension.
The amount of the sulfate ion existed before calcining is generally by weight from 1% to 50%, usually by weight from 5% to 30%, and more generally by weight from 10% to 25%, wherein wt per-cent is based on the weight of the soild oxide before calcining.Once after the vitriol dipping, the sulfation oxide compound can come dry by any currently known methods in this area, include but not limited to that air exhaust filtering (suction filtration) evaporates afterwards, dry under vacuum, spraying drying and similar approach, although get started calcining step, be also possible.
Except by the electrophilic component, for example halogenide or sulfate ion are processed, solid inorganic oxide of the present invention can optionally be processed by source metal, comprises metal-salt or metal-containing compound.In one aspect of the invention, these compounds can be added into or be impregnated on soild oxide with the solution form, and are converted into subsequently the metal (supported metal) of carried after calcining.Therefore, solid inorganic oxide can also contain metal, is selected from zinc, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum or their any combination.For example zinc can be used to flood soild oxide, because it provides good catalyst activity and low cost.Before with electrophilic anionic treatments soild oxide, afterwards or simultaneously, soild oxide can be processed with metal-salt or metal-containing compound.
In addition, can use any method with metal impregnation soild oxide material.By the method, oxide compound is contacted with source metal, source metal is generally salt or metal-containing compound, and described method includes but not limited to gelation, gelation, a kind of compound are impregnated into another kind of upper and similar approach altogether.After any contact method, the contact mixture of oxide compound, electrophilic negatively charged ion and metal ion is generally calcined.Alternatively, soild oxide material, electrophilic negative ion source and metal-salt or metal-containing compound are contacted simultaneously and are calcined.
In another aspect, metallocene compound can contact the first paragraph time with the organoaluminum promotor in advance with olefinic monomer, then makes this mixture contact with acidic activator-carrier.Once the pre-contact mixture of metallocene, monomer, organoaluminum promotor with after acidic activator-carrier contacts, also comprises that the composition of acidic activator-carrier is called as " rear contact " mixture.Be added into before carrying out the reactor of polymerization process, can making this rear contact mixture keep the further contact second segment time.
Preparation can be used in the whole bag of tricks of the soild oxide activator-carrier in the present invention and be reported.For example, United States Patent (USP) the 6th, 107,230,6,165,929,6,294,494,6,300,271,6,316,553,6,355,594,6,376,415,6,391,816,6,395,666,6,524,987 and 6,548, No. 441 this class methods have been described, they each at this, all be incorporated herein by reference.
Optional aluminoxane catalyst
In one aspect, the invention provides catalyst composition, it comprises at least one metallocene, at least one organo-aluminium compound, at least one alkene or ethane monomer and at least one acidic activator-carrier, and also comprises optional promotor.On the one hand, optional promotor can be at least one aikyiaiurnirsoxan beta, at least one organoboron compound, at least one ionizing ionic compound or their arbitrary combination.On the other hand, this optional promotor can be used in pre-contact procedure, in rear contact procedure or in two steps.In addition, the arbitrary combination of promotor can be used in arbitrary step or two steps in.
Aikyiaiurnirsoxan beta is also referred to as poly-(alkyl aluminum oxide) (poly (hydrocarbyl aluminum oxides)) or simply be called Organoaluminoxy alkane.Usually, other catalyst component is contacted in the saturated hydrocarbons compound solvent with aikyiaiurnirsoxan beta, although can use any solvent to the basic inertia of product of reactant, intermediate and activation step.Formed catalyst composition can be collected by method known to persons of ordinary skill in the art in this way, include but not limited to filter, or catalyst composition can be introduced in polymerization reactor without separation.
Aluminium alkoxide compound of the present invention is oligomeric aluminum compound, and wherein said aluminium alkoxide compound can comprise linear structure, ring-type or cage structure, or usually, the mixture of all these three kinds of structures.Ring-type aluminium alkoxide compound with following formula be the present invention includes:
Figure A20058002592600341
wherein
R is the straight or branched alkyl with 1 to 10 carbon atom, and n is 3 to 10 integer.Be presented at this (AlRO) npart has also formed the repeating unit in the line style aikyiaiurnirsoxan beta.Therefore, the line style aikyiaiurnirsoxan beta that has a following formula also be the present invention includes:
wherein
R is the straight or branched alkyl with 1 to 10 carbon atom, and n is 1 to 50 integer.
In addition, aikyiaiurnirsoxan beta also has formula R t 5m+ αr b m-αal 4mo 3mcage structure, wherein m is 3 or 4, and α=n al (3)-n o (2)+ n o (4); N wherein al (3)the number of three-fold coordination aluminium atom, n o (2)the number of two coordination Sauerstoffatoms, n o (4)the number of 4 coordination Sauerstoffatoms, R trepresent the end alkyl group, R brepresent the bridging alkyl group; Wherein R is the straight or branched alkyl with 1 to 10 carbon atom.
Therefore, the aikyiaiurnirsoxan beta that can be used as the optional promotor in the present invention generally by formula such as (R-Al-O) n, R (R-Al-O) nalR 2reach similar formula and mean, wherein the R group is generally straight or branched C 1-C 6alkyl, for example methyl, ethyl, propyl group, butyl, amyl group or hexyl, wherein general from 1 to 50 the integer that means of n.In one embodiment, aluminium alkoxide compound of the present invention includes but not limited to methylaluminoxane, ethylaluminoxane, n-propyl aikyiaiurnirsoxan beta, sec.-propyl aikyiaiurnirsoxan beta, normal-butyl alumina alkane, tertiary butyl aikyiaiurnirsoxan beta, sec-butyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide, 1-amyl group aikyiaiurnirsoxan beta, 2-amyl group aikyiaiurnirsoxan beta, 3-amyl group aikyiaiurnirsoxan beta, isopentyl aikyiaiurnirsoxan beta, neo-pentyl aikyiaiurnirsoxan beta or their composition.
Although have the Organoaluminoxy alkane of dissimilar R group, can be the present invention includes, methylaluminoxane (MAO), ethylaluminoxane or isobutyl aluminium alkoxide are the optional promotors of typical case be used in catalyst composition of the present invention.Prepared from trimethyl aluminium, triethyl aluminum or triisobutyl aluminium respectively by these aikyiaiurnirsoxan beta, and sometimes be called as respectively poly-(methyl oxidation aluminium) (poly (methyl aluminum oxide)), poly-(ethyl aluminum oxide) (poly (ethyl aluminum oxide) and poly-(isobutyl-aluminum oxide) (poly (isobutyl aluminumoxide)).Use aikyiaiurnirsoxan beta also within the scope of the invention together with trialkylaluminium, for example be disclosed in United States Patent (USP) the 4th, in 794, No. 096, it all is incorporated herein by reference at this.
The present invention considers at aikyiaiurnirsoxan beta formula (R-Al-O) nand R (R-Al-O) nalR 2in a lot of values of n, and preferably, n is at least 3.Yet, depend on how Organoaluminoxy alkane is produced, stores and uses, in the single sample of aikyiaiurnirsoxan beta, the value of n can be variable, and such combination of Organoaluminoxy alkane is included in method and composition of the present invention.
When preparation comprises the catalyst composition of the present invention of optional aikyiaiurnirsoxan beta, the aluminium in aikyiaiurnirsoxan beta and the mol ratio of the metallocene in composition are generally 1: 10 to 100,000: 1.In one aspect, the aluminium in aikyiaiurnirsoxan beta and the mol ratio of the metallocene in composition are generally 5: 1 to 15,000: 1.The quantity that adds the optional aikyiaiurnirsoxan beta in polymerization zone is to be positioned at 0.01mg/L to 1000mg/L, 0.1mg/L to 100mg/L or the 1mg/L amount to about 50mg/L scope.
Can prepare organic aikyiaiurnirsoxan beta by the whole bag of tricks well known in the art.Example prepared by Organoaluminoxy alkane is disclosed in United States Patent (USP) the 3rd, and 242,099 and 4,808, in No. 561, it all is incorporated herein by reference at this.The example how aikyiaiurnirsoxan beta is produced is as follows.Be dissolved in water in inert organic solvents can with alkylaluminium cpd AlR for example 3react and the Organoaluminoxy hydride compounds of formation expectation.Although do not expect to be bound by this statement, it is believed that, this kind of synthetic method can provide line style and ring-type (R-Al-O) nthe mixture of aikyiaiurnirsoxan beta kind, these two kinds of aikyiaiurnirsoxan beta be the present invention includes.Alternatively, by making for example AlR of alkylaluminium cpd 3with salt hydrate for example hydrated copper sulfate in inert organic solvents, react, can prepare organic aikyiaiurnirsoxan beta.
Optional organic boron promotor
In one aspect, the invention provides catalyst composition, it comprises at least one metallocene, at least one organo-aluminium compound, at least one alkene or ethane monomer and at least one acidic activator-carrier, and also comprises optional promotor.On the one hand, optional promotor can be at least one aikyiaiurnirsoxan beta, at least one organoboron compound, at least one ionizing ionic compound or their arbitrary combination.On the other hand, this optional promotor can be used in pre-contact procedure, in rear contact procedure or in two steps.In addition, the arbitrary combination of promotor can be used in arbitrary step or two steps in.
In one aspect, organoboron compound comprises neutral boron compound, borate or their combination.For example, organoboron compound of the present invention can comprise fluorine organic boron (fluoroorgano boron) compound, fluorine organic borate (fluoroorgano borate) compound or their combination.Can use any fluorine organic boron as known in the art or fluorine organic boronic salt compound.Term fluorine organoboron compound has its common meaning, and the form of referring to is BY 3neutral compound.Term fluorine organic boronic salt compound also has its common meaning, and the form that refers to is for [positively charged ion] +[BY 4] -the single anion salt of fluorine organoboron compound, wherein organic group is fluoridized in the Y representative.For simplicity, fluorine organic boron and fluorine organic boronic salt compound generally are generically and collectively referred to as organoboron compound, or based on context need to be called as any title.
The example that can be used as the fluorine organic boronic salt compound of the promotor in the present invention comprises, but be not limited to fluoro aryl borate (fluorinated aryl borates), N for example, accelerine four (pentafluorophenyl group) borate (N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate), triphenylcarbenium
Figure 10003_2
four (pentafluorophenyl group) borate (triphenylcarbenium tetrakis (pentafluorophenyl) borate), four (pentafluorophenyl group) lithium tetraborate (lithium tetrakis (pentafluorophenyl) borate), N, accelerine four [3, two (trifluoromethyl) phenyl of 5-] borate (N, N-dimethylanilinium tetrakis[3,5-bis (trifluoromethyl) phenyl] borate), triphenylcarbenium four [3,5-two (trifluoromethyl) phenyl] borate (triphenylcarbeniumtetrakis[3,5-bis (trifluoromethyl) phenyl] borate) and analogue, comprise their mixture.The example that can be used as the fluorine organoboron compound of the promotor in the present invention includes but not limited to three (pentafluorophenyl group) boron (tris (pentafluorophenyl) boron), three [3, two (trifluoromethyl) phenyl of 5-] boron (tris[3,5-bis (trifluoromethyl) phenyl] boron) and analogue, comprise their mixture.
Although do not expect to be bound by following theory, these examples of fluorine organic borate and fluorine organoboron compound and related compound are considered to when formed " weak coordination (weakly-coordinating) " negatively charged ion when organometallic compound is combined, as at United States Patent (USP) 5,919, open in 983, it all is incorporated herein by reference at this.
Generally speaking, any amount of organoboron compound can be used in the present invention.In one aspect, the mol ratio of the metallocene compound in organoboron compound and composition is 0.1: 1 to 10: 1.Usually, as the amount of the fluorine organic boron of the promotor of metallocene or fluorine organic boronic salt compound every mole of metallocene compound be 0.5 mole to the scope of 10 moles of boron compounds.In one aspect, as the amount of the fluorine organic boron of the promotor of metallocene or fluorine organic boronic salt compound every mole of metallocene compound be 0.8 mole to the scope of 5 moles of boron compounds.
Optional ionizing ionic compound promotor
In one aspect, the invention provides catalyst composition, it comprises at least one metallocene, at least one organo-aluminium compound, at least one alkene or ethane monomer and at least one acidic activator-carrier, and also comprises optional promotor.On the one hand, optional promotor can be at least one aikyiaiurnirsoxan beta, at least one organoboron compound, at least one ionizing ionic compound or their arbitrary combination.On the other hand, this optional promotor can be used in pre-contact procedure, in rear contact procedure or in two steps.In addition, the arbitrary combination of promotor can be used in arbitrary step or two steps in.The example of ionizing ionic compound is disclosed in United States Patent (USP) the 5th, and 576,259 and 5,807, in No. 938, their each piece of writing all is incorporated herein by reference at this.
The ionizing ionic compound is the ionic compound that can work to strengthen the catalyst composition activity.Although be not bound by theory, it is believed that, described ionizing ionic compound can react with metallocene compound and metallocene is converted into to the cationic metallocene compound.Equally, although do not expect to be bound by theory, it is believed that, this ionizing ionic compound, by completely or partially from metallocene, extracting anion ligand, can play a part the ionizing compound, and described anion ligand may right and wrong-η 5-alkadienyl part, for example (X 3) or (X 4).Yet the ionizing ionic compound is activator, no matter it is the ionization metallocene, in the mode that forms ion pair, captures (X 3) or (X 4) part, the metal in the weakening metallocene-(X 3) or metal-(X 4) key, simply with (X 3) or (X 4) the part coordination, or any mechanism that other is activated.In addition, the ionizing ionic compound needn't only activate metallocene.With the catalyst composition that contains the catalyst composition that does not comprise any ionizing ionic compound, compare, the mobilizing function of ionizing ionic compound is obvious generally on the activity that strengthens catalyst composition.
The example of ionization ionic compound includes but not limited to following compound: three (normal-butyl) ammonium four (p-methylphenyl) borate, three (normal-butyl) ammonium four (tolyl) borate, three (normal-butyl) ammonium four (2, the 4-dimethyl) borate, three (normal-butyl) ammonium four (3, the 5-3,5-dimethylphenyl) borate, three (normal-butyl) ammonium four [3, two (trifluoromethyl) phenyl of 5-] borate, three (normal-butyl) ammonium four (pentafluorophenyl group) borate, N, accelerine four (p-methylphenyl) borate, N, accelerine four (tolyl) borate, N, accelerine four (2, the 4-3,5-dimethylphenyl) borate, N, accelerine four (3, the 5-3,5-dimethylphenyl) borate, N, accelerine four [3, two (trifluoromethyl) phenyl of 5-] borate, N, accelerine four (pentafluorophenyl group) borate, triphenylcarbenium
Figure 10003_4
four (p-methylphenyl) borate, triphenylcarbenium
Figure 10003_5
four (tolyl) borate, triphenylcarbenium
Figure 10003_6
four (2,4-3,5-dimethylphenyl) borate, triphenylcarbenium four (3,5-3,5-dimethylphenyl) borate, triphenylcarbenium four [two (trifluoromethyl) phenyl of 3,5-] borate, triphenylcarbenium
Figure 10003_9
four (pentafluorophenyl group) borate,
Figure 10003_10
Figure 10003_11
four (p-methylphenyl) borate,
Figure 10003_12
four (tolyl) borate,
Figure 10003_14
four (2,4-3,5-dimethylphenyl) borate,
Figure 10003_16
four (3,5-3,5-dimethylphenyl) borate,
Figure 10003_18
Figure 10003_19
four [two (trifluoromethyl) phenyl of 3,5-] borate,
Figure 10003_20
Figure 10003_21
four (pentafluorophenyl group) borate, four (pentafluorophenyl group) lithium borate, four (phenyl) lithium borate, four (p-methylphenyl) lithium borate, four (tolyl) lithium borate, four (2,4-3,5-dimethylphenyl) lithium borate, four (3,5-3,5-dimethylphenyl) lithium borate, LiBF4, four (pentafluorophenyl group) Boratex, four (phenyl) Boratex, four (p-methylphenyl) Boratex, four (tolyl) Boratex, four (2,4-3,5-dimethylphenyl) Boratex, four (3,5-3,5-dimethylphenyl) Boratex, sodium tetrafluoroborate, four (pentafluorophenyl group) potassium borate, four (phenyl) potassium borate, four (p-methylphenyl) potassium borate, four (tolyl) potassium borate, four (2,4-3,5-dimethylphenyl) potassium borate, four (3,5-3,5-dimethylphenyl) potassium borate, potassium tetrafluoroborate, three (normal-butyl) ammonium four (p-methylphenyl) aluminate, three (normal-butyl) ammonium four (tolyl) aluminate, three (normal-butyl) ammonium four (2,4-dimethyl) aluminate, three (normal-butyl) ammonium four (3,5-3,5-dimethylphenyl) aluminate, three (normal-butyl) ammonium four (pentafluorophenyl group) aluminate, DMA four (p-methylphenyl) aluminate, DMA four (tolyl) aluminate, DMA four (2,4-3,5-dimethylphenyl) aluminate, DMA four (3,5-3,5-dimethylphenyl) aluminate, DMA four (pentafluorophenyl group) aluminate, triphenylcarbenium four (p-methylphenyl) aluminate, triphenylcarbenium
Figure 10003_23
four (tolyl) aluminate, triphenylcarbenium
Figure 10003_24
four (2,4-3,5-dimethylphenyl) aluminate, triphenylcarbenium
Figure 10003_25
four (3,5-3,5-dimethylphenyl) aluminate, triphenylcarbenium
Figure 10003_26
four (pentafluorophenyl group) aluminate,
Figure 10003_27
four (p-methylphenyl) aluminate, four (tolyl) aluminate,
Figure 10003_32
four (2,4-3,5-dimethylphenyl) aluminate,
Figure 10003_33
Figure 10003_34
four (3,5-3,5-dimethylphenyl) aluminate,
Figure 10003_36
four (pentafluorophenyl group) aluminate, four (pentafluorophenyl group) lithium aluminate, four (phenyl) lithium aluminate, four (p-methylphenyl) lithium aluminate, four (tolyl) lithium aluminate, four (2, the 4-3,5-dimethylphenyl) lithium aluminate, four (3, the 5-3,5-dimethylphenyl) lithium aluminate, the tetrafluoro lithium aluminate, four (pentafluorophenyl group) sodium aluminate, four (phenyl) sodium aluminate, four (p-methylphenyl) sodium aluminate, four (tolyl) sodium aluminate, four (2, the 4-3,5-dimethylphenyl) sodium aluminate, four (3, the 5-3,5-dimethylphenyl) sodium aluminate, the tetrafluoro sodium aluminate, four (pentafluorophenyl group) potassium aluminate, four (phenyl) potassium aluminate, four (p-methylphenyl) potassium aluminate, four (tolyl) potassium aluminate, four (2, the 4-3,5-dimethylphenyl) potassium aluminate, four (3, the 5-3,5-dimethylphenyl) potassium aluminate, ptfe aluminum potassium.Yet the ionizing ionic compound is not limited to these in the present invention.
The preparation of catalyst composition
According to the present invention, can be by such method Kaolinite Preparation of Catalyst composition, described method comprises makes the organoaluminum cocatalyst compound contact in advance one period working lipe with alkene or alkynes with organometallic compound, then makes this mixture contact one period working lipe with activator-carrier.On the one hand, the method for preparing catalyzer of the present invention can be carried out under inert atmosphere and substantially anhydrous conditions.Therefore, when reaction starts, the basic anaerobic of atmosphere and basically anhydrous, to prevent catalyst deactivation.In one aspect of the invention, for example, 1-hexene, triethyl aluminum and luxuriant zirconium for example two (indenyl) zirconium dichlorides or two (cyclopentadienyl) zirconium dichloride are contacted at least 30 minutes in advance, before this occurs in and makes this mixture and fluorinated silica-aluminum oxide activating agent-carrier contacts.Once this pre-contact mixture contacts with activator-carrier, after this, contact mixture is allowed to keep in touch 1 minute to 24 hours, is generally 5 minutes to 5 hours, is more typically 10 minutes to 1 hour, then in polymerization process, uses this mixture.
Usually, the mixture of metallocene, alkene or alkyne monomer and organo-aluminium compound, with before activator-carrier contacts, be called as " pre-contact " mixture at it.Therefore, the component of pre-contact mixture is called as pre-contact metallocene, contacts alkene or alkyne monomer in advance and contact in advance organo-aluminium compound.The mixture of pre-contact mixture and acidic activator-carrier, the mixture of metallocene, alkene or alkyne monomer, organo-aluminium compound and acidic activator-carrier, be called as " rear contact " mixture.Therefore, the component of rear contact mixture be called as rear contact metallocene, rear contact alkene or alkyne monomer, rear contact organo-aluminium compound and after contact acidic activator-carrier.
In one aspect of the invention, when pre-contact mixture comprises various ingredients except metallocene, alkene or alkyne monomer and organo-aluminium compound, can obtain the catalytic activity of enhancing.In this respect, the change of component of pre-contact mixture and rear contact mixture, make can to catalyst composition to reach expectation active, or provide specific polymerization process.
Can carry out in many ways pre-contact procedure, include but not limited to blending.And each of organo-metallic, monomer and organoaluminum cocatalyst compound can be fed in reactor separately, or the various combination of these compounds contacts with each other before can further contacting in reactor.Alternatively, all three kinds of compounds can contact together before being introduced into reactor.Usually, the mixture of metallocene, alkene or alkynes and organo-aluminium compound can be in independent reactor by pre-contact number minute to a few hours, this occurs in and this mixture is contacted and before forming afterwards contact mixture with activator-carrier.This pre-contact procedure is carried out usually under inert atmosphere.In addition, pre-contact procedure can follow stirring, stirring, heating, cooling, sonication, shake, under pressure, under room temperature, carry out at inert solvent (being generally hydrocarbon) and conditions of similarity.Yet, because pre-contact procedure can only be undertaken by making component remain substantially undisturbed, this type of condition is nonessential.
In another aspect of this invention, at first by being contacted before injecting reactor, organo-aluminium compound, alkene or acetylene and organo-metallic (being generally metallocene) compound prepares pre-contact mixture, usually contact is 1 minute to 9 days, more generally 1 minute to 24 hours.The component of pre-contact mixture generally contacts at the temperature of 10 ℃ to 200 ℃, usually from 15 ℃ to 80 ℃.Then, make this pre-contact mixture contact placement with acidic activator-carrier, described acidic activator-carrier is generally fluorinated silica-aluminum oxide activating agent-carrier as disclosed herein, to form rear contact mixture.
Arbitrarily for a long time prepare rear contact mixture with contacting under pressure and mixing acidic activator-carrier with pre-contact mixture by contacting fully with the arbitrary temp reacted between the contact mixture component after making.For example, usually make this rear contact mixture keep in touch 1 minute to 24 hours, be generally 5 minutes to 5 hours, and be more typically 10 minutes to 1 hour, then in polymerization process, use this mixture.Once acidic activator-carrier is with after pre-contact mixture contacts for some time, said composition comprise rear contact organometallic compound (usually, metallocene), rear contact organo-aluminium compound, rear contact alkene or alkynes and after contact acidic activator-carrier (being generally fluorinated silica-aluminum oxide).Usually, rear contact acidic activator-carrier accounts for the majority of composition by weight.Often, the specific nature of the final component of prepared catalyzer is unknown as described in this article, and therefore catalyst composition of the present invention is described as and comprises rear contact compound and component.In addition, because the definite order of contact can change, so it is believed that the component of the most applicable description composition of this term.
On the one hand, the rear contact procedure that wherein pre-contact mixture contacts placement with acidic activator-carrier is carried out usually in inert atmosphere.Usually in the scope of 0.1 hour to 24 hours, and be more usually in 0.1 to 1 hour the duration of contact between acidic activator-carrier and pre-contact mixture.This mixture can be heated to 0
Figure 10003_37
(17.7 ℃) are to 150
Figure 10003_38
temperature between (65.56 ℃).If mixture is heated fully, 40
Figure 10003_39
(4.44 ℃) are to 95
Figure 10003_40
temperature between (35 ℃) is typical.Although do not expect to be bound by theory, these conditions are believed to be helpful in the deposition of catalyzer on acidic activator-carrier of catalytically effective amount.
Usually, at a temperature, heated for some time, this time length is enough to make pre-contact mixture and acidic activator-carrier can adsorb, flood or interact, and makes the part of pre-contact component be fixed, absorption or deposited thereon.For example, on the one hand, by make 1-hexene, triethyl aluminum and luxuriant zirconium for example two (indenyl) zirconium dichlorides or two (cyclopentadienyl) zirconium dichloride contact at least 30 minutes in advance, make afterwards this pre-contact mixture contact at least 10 minutes with fluorinated silica-aluminum oxide activating agent-carrier extremely can to reach 1 hour to prepare catalyst composition of the present invention with the formation active catalyst.
More than one metallocene can be used in catalyst composition of the present invention and method.When catalyst composition comprises more than one metallocenes, metallocene compound is used in one or more pre-contact mixture.Therefore, these multiple metallocenes can be used in identical pre-contact mixture, then be used in identical rear contact mixture, they can be used in different pre-contact mixture, then described pre-contact mixture is used to prepare identical rear contact mixture, perhaps they can be used in different pre-contact mixture and different rear contact mixture in, then described rear contact mixture is introduced in polymerization reactor.
On the one hand, the mol ratio of organo-metallic or metallocene compound and organo-aluminium compound is 1: 1 to 1: 10,000, be generally 1: 1 to 1: 1, and 000, and be more typically 1: 1 to 1: 100.These mol ratios have reflected the mol ratio of metallocene compound and the organo-aluminium compound total amount in pre-contact mixture and rear contact mixture.
Generally speaking, in pre-contact mixture the mol ratio of alkene or alkyne monomer and organo-metallic or metallocene compound be 1: 10 to 100,000: 1, be generally 10: 1 to 1,000: 1.
In another aspect of this invention, the weight ratio of acidic activator-carrier and organo-aluminium compound usually at 1: 5 to 1,000: 1 scope, typically be 1: 3 to 100: 1, be more typically 1: 1 to 50: 1.In still another aspect of the invention, the weight ratio of metallocene and acidic activator-carrier is generally 1: 1 to 1: 10, and 000,000, more generally from 1: 10 to 1: 100,00, even more generally from 1: 20 to 1: 1000.These ratios that relate to acidic activator-carrier are based on the amount that is added into to form rear contact mixture and the component of catalyst composition is provided.
It is necessary that one aspect of the present invention is that aikyiaiurnirsoxan beta is not formed in this disclosed catalyst composition, it is characterized in that allowing lower polymer production cost.Therefore, the present invention only uses AlR 3the type organo-aluminium compound, it does not activate metallocene catalyst in the mode identical with Organoaluminoxy alkane.In addition, expensive borate compound or MgCl 2to forming catalyst composition of the present invention, be not essential, although aikyiaiurnirsoxan beta, borate compound, MgCl 2or their combination can optionally be used in aspects more of the present invention.Yet another aspect of the present invention is the use of optional promotor, includes but not limited at least one aikyiaiurnirsoxan beta, at least one organoboron compound, at least one ionizing ionic compound or their arbitrary combination.
It is believed that, may be relevant with the formation of organoaluminum metal ring compound (organoaluminum metallacylic compound) from the beyond thought enhancing of the viewed catalytic activity of some catalyst components of pre-contact, this forms the aluminium pentamethylene (aluminacyclo-pentanes based on reaction scheme scheme 1 below authority for the report, synthesizing ACPs), diagram 1, used (η 5-C 5h 5) 2zrCl 2and CH 2=CHCH 2r (R=C 3h 7, C 5h 11or C 8h 17), η wherein 5-C 5h 5=Cp.
Scheme 1
Figure A20058002592600411
A reaction scheme of producing ACPs is described in U.M.Dzhemilev and A.G.Ibragimov, Journal of Organometallic Chemistry, 1994,466, in 1-4, its with the bibliography of institute's reference therein with quote together with, each all is incorporated herein by reference.Other reaction scheme of producing ACPs is described in Khalikov, L.M.; Parfenova, L.V.; Rusakov, S.V.; Ibragimov, A.G.; Dzhemilev, U.M.Russian Chemical Bulletin, International Addition 2000,49, (12), in 205 1-2058.Also referring to Negishi, E.; Kondakov, Denis, Y.; Choueiry, D.; Kasai, K.; Takahashi, T.Journal ofthe American Chemical Society 1996,118,9577-9588, each all is incorporated in this as reference.According to scheme 1, when organo-metallic (being generally metallocene) compound contacts with alkene in advance with organo-aluminium compound, the aluminium pentamethylene can form.Although do not expect to be bound by this statement, according to this reaction scheme and at Dzhemilev, U.M.; Ibragimov, A.G.Russian Chemical Reviews 2000,69, (2) the similar scheme of describing in 121-135, when organo-metallic (being generally metallocene) compound contacts with alkynes in advance with organo-aluminium compound, aluminium cyclopentenes (aluminacyclopentene) can form.The alkene and the alkynes mixture that are desirably in pre-contact mixture form aluminium pentamethylene and aluminium cyclopentenes in a similar manner.
According to Khalikov, L.M.; Parfenova, L.V.; Rusakov, S.V.; Ibragimov, A.G.; Dzhemilev, U.M.Russian Chemical Bulletin, International Addition 2000,49, (12), 2051-2058, and the bibliography of wherein reference and quoting, the possible mechanism that exists several schemes 1 to work, one of them is described in scheme 2.Notice that only a positional isomers (regioisomer) of intermediate B is illustrated, cause aluminium pentamethylene (ACP) the positional isomers C illustrated.
Scheme 2
Yet this scheme also is supposed to provide the aluminium pentamethylene of some alpha-substitution, structure D is shown in herein:
Figure A20058002592600422
Therefore, for any particular compound disclosed herein, any general structure formula presented also comprises all isomer, comprises and can be derived from all positional isomerss specified substituent group or specific reaction scheme, as the requirement of context institute.
Another aspect of the present invention is catalyst composition, and it comprises the metal ring pentane (metallacyclopentane) of aluminium pentamethylene or metallocene, for example zirconium pentamethylene (zirconacyclopentane).Therefore, the present invention includes the catalyst composition that comprises pre-contact metallocene, contacts in advance alkene or alkynes, rear contact acidic activator-carrier and aluminium pentamethylene.The present invention also comprises the catalyst composition that comprises pre-contact metallocene, the metal ring pentane that contacts in advance alkene or alkynes, rear contact acidic activator-carrier and metallocene or metal ring amylene (metallacyclopentene).
Equally, although do not expect to be bound by theoretical explanation, top reaction scheme also can explain that triethyl aluminum (TEA) is to forming the good and trimethyl aluminium (TMA) of the pre-contact solution work bad reason of working.As shown in scheme 2, if the alkylaluminium cpd be used in pre-contact mixture comprises β-hydrogen atom, when being coordinated in organometallic compound, these alkyl groups can participate in shown β-H and eliminate process, thus the zirconium pentamethylene and the ACP that form zirconium-aluminum compound and obtain.The ethyl group of TEA has β-hydrogen atom, and the methyl group of TMA does not have β-hydrogen atom.
Although do not expect to be bound by theory, it is believed that, when in solution, having two kinds of alkene, can produce different aluminium pentamethylene (ACPs).For example,, if both there had been CH in solution 2=CHCH 2there is again CH in R 2=CH 2, the other aluminium pentamethylene that is similar to C and D is considered to containing CH 2=CHCH 2r and CH 2=CH 2pre-contact solution in be can and (accessible) (no matter ethene is to be introduced into or to be derived from AlEt 3), it can also produce following aluminium pentamethylene E-H, is derived from the same coupling (homocoupling) of two alkene identical on single metal:
Figure A20058002592600431
As illustrated as scheme 2, these different aluminum pentamethylene will produce from similar zirconium pentamethylene.
On the other hand, the present invention includes catalyst composition, it comprises pre-contact metallocene, contacts alkene or alkynes, rear contact acidic activator-carrier and aluminium pentamethylene in advance.Therefore, catalyst composition of the present invention can comprise aluminium pentamethylene (E, F, G, H) or aluminium cyclopentenes (I), no matter they are to be produced by reaction scheme disclosed herein, or independent preparation.Similarly, the present invention also comprises catalyst composition, and it comprises pre-contact metallocene, contacts alkene or alkynes, rear contact acidic activator-carrier and zirconium ring (zirconacyclic) kind in advance.As shown in scheme 2 and the above-mentioned bibliography of quoting, this ring-type organo-metallic kind can be the zirconium pentamethylene (J) of any metallocene of using of the present invention or zirconium cyclopentenes (zirconacyclopentene) (K), no matter they are to be produced by top disclosed reaction scheme, or independent preparation.
Figure A20058002592600432
By the gas-chromatography of aluminium pentamethylene hydrolysate, and emit by gas (ethane) when TEA is used as organo-aluminium compound, detect the formation of aluminium pentamethylene after metallocene compound, organo-aluminium compound and alkene are contacted in advance in the present invention.Therefore, an aspect of of the present present invention comprises the organic aluminum metal ring compound of preparation, based at U.M.Dzhemilev and A.G.Ibragimov, Journal of Organometallic Chemistry, 1994, synthesizing of the aluminium pentamethylene of reporting in 466,1-4, and use the reaction mixture that comprises the aluminium pentamethylene to replace pre-contact mixture according to this reaction.
In another aspect of this invention, the change of component of pre-contact mixture and rear contact mixture, make resulting catalyst composition be suitable for the activity of expecting, or the method for Kaolinite Preparation of Catalyst composition can provide the polymerization process of expectation.For example, on the one hand, catalyst composition of the present invention comprise pre-contact metallocene, in advance contact organo-aluminium compound, rear contact alkene or alkynes and after contact acidic activator-carrier.On the other hand, catalyst composition of the present invention comprise pre-contact metallocene, rear contact organo-aluminium compound, in advance contact alkene or alkynes and after contact acidic activator-carrier.Aspect another, catalyst composition of the present invention comprises pre-contact metallocene, rear contact organo-aluminium compound, contacts alkene or alkynes in advance and contact in advance acidic activator-carrier.Still on the other hand, catalyst composition of the present invention comprises pre-contact metallocene, contacts alkene or alkynes, rear contact acidic activator-carrier and aluminium pentamethylene or aluminium cyclopentenes in advance.In in these areas each, the change of component of pre-contact or rear contact mixture wherein, in pre-contact or rear contact mixture the relative quantity of each component usually with comprise pre-contact metallocene, in advance contact organo-aluminium compound, in advance contact alkene or alkynes and contact afterwards the scope that the catalyst composition of acidic activator-carrier is identical in those scopes disclosed herein within.
The application of catalyst composition in polymerization process
On the one hand, catalyst composition of the present invention can have than using identical component but not comprise the higher activity of catalyst composition of pre-contact organometallic compound, organo-aluminium compound and alkene or alkyne monomer.
With the polymerization of catalyzer of the present invention, can carry out in any mode known in the art.This type of polymerization process includes but not limited to slurry polymerization, vapour phase polymerization, solution polymerization and similar approach, comprises their multiple reactor combination.Therefore, can use any polymerization zone (polymerization zone) as known in the art, as to produce the polymkeric substance that contains ethene.For example, the reactor of stirring can be used to batch process (batchprocess), or reaction can be carried out in loop reactor or in continuous-stirring reactor continuously.
After catalyst activation, catalyst composition is used to ceridust or copolymerization of ethylene and comonomer.In one aspect, typical polymerization process is slurry phase polymerisation process (being also referred to as particulate state method (particle form process)), it is known in the art, and be disclosed in for example U.S. Patent number 3,248, in 179, this patent all is incorporated herein by reference at this.Other polymerization process of the present invention about slurry process (slurry processes) is that those uses are disclosed in U.S. Patent number 3,248, loop reactor type in 179, and those methods of using in numerous reactors of series winding, parallel or its combination, wherein in different reactors, reaction conditions is different, and it also all is incorporated herein by reference at this.
In one aspect, polymerization temperature of the present invention can be at 60 ℃ to 280 ℃, and in one aspect of the method, polymeric reaction temperature can be at 70 ℃ to 110 ℃.
On the other hand, polyreaction generally occurs in inert atmosphere, that is, in the atmosphere that substantially there is no oxygen and under substantially anhydrous environment, therefore, in the situation that there is not water, reaction starts.Therefore, for example nitrogen or the dry argon of drying generally are used in polymerization reactor dry inert atmosphere.
Still on the other hand, pre-treatment pressure can be any pressure that does not stop this pre-treatment step, and is generally to be suitable for for example pressure of the formation of aluminium pentamethylene (ACPs) of organoaluminum metal ring compound after pre-contact metallocene, organo-aluminium compound and alkene.Pre-treatment pressure usually but must be lower than polymerization pressure, and generally at normal atmosphere to the scope of 100psig (791 kPas (kPa)).On the one hand, pre-treatment pressure is from normal atmosphere to 50psig (446kPa).
Still on the other hand, polymerization pressure can be any pressure that does not stop this polyreaction, and generally under the pressure higher than pre-treatment pressure, carries out.In one aspect, polymerization pressure can be from normal atmosphere to 1000psig (7000kPa).In one aspect of the method, polymerization pressure can be from 50psig (446kPa) to 800psig (5620kPa).In addition, hydrogen can be used in polymerization process of the present invention, to control polymericular weight.
When the multipolymer of ethene produced according to the present invention, the amount formed with the polymkeric substance that enough produces expectation is introduced reaction zone by comonomer.Typical multipolymer forms the comonomer that gross weight based on monomer and comonomer is generally 0.01 to 10 weight percent, yet, depend on that the composition of multipolymer specification and expectation, this multipolymer form to change outside this scope.Therefore, can use the multipolymer of any amount, this amount is enough to provide described polymkeric substance to form in produced multipolymer.
With the polymerization of catalyzer of the present invention, can carry out in any mode known in the art.These class methods that can be polymkeric substance by monomer polymerization include but not limited to slurry polymerization, vapour phase polymerization, solution polymerization and the combination of their multiple reactor.Therefore, can use any polymerization zone as known in the art, as to produce the polymkeric substance that contains alkene.On the one hand, for example, stirred reactor can be used to batch process, or reaction can be carried out in loop reactor or in continuous-stirring reactor continuously.On the other hand, for example, use slurry phase polymerisation process to carry out polymerization disclosed herein in loop reaction zone.The suitable thinner be used in slurry polymerization is known in the art, and to be included under reaction conditions be the hydro carbons of liquid.Be used in term " thinner (diluent) " the definiteness inert substance that differs in the disclosure, because this term is intended to comprise compound and the composition that can contribute to polymerization process.The example that can be used as the hydro carbons of thinner includes but not limited to hexanaphthene, Trimethylmethane, normal butane, propane, Skellysolve A, iso-pentane, neopentane and normal hexane.Usually, Trimethylmethane is used as the thinner in the slurry polymerization process.The example of this technology is in U.S. Patent number 4,424,341; 4,501,885; 4,613,484; 4,737,280; With 5,597, find in 892, each piece of writing wherein all is incorporated herein by reference at this.
For the present invention's purpose, the term polymerization reactor comprises any polymerization reactor known in the art or polymerization reactor system, and it can polymerization of olefin monomers and produces homopolymer of the present invention or multipolymer.This type of reactor can comprise slurry-phase reactor, Gas-phase reactor, solution reactor or their any combination.Gas-phase reactor can comprise fluidized-bed reactor or tubular reactor.Slurry-phase reactor can comprise vertical loop (vertical loops) or horizontal loop (horizontal loops).Solution reactor can comprise stirring tank or autoclave reactor (autoclave reactors).
Be applicable to feed system, at least one reactor system, at least one polymer recovery system or their any suitable combination that polymerization reactor of the present invention can comprise at least one raw material feed system, at least one catalyzer or catalyst component.May further include any of catalyzer storage system, extrusion system (extrusion system), cooling system, diluent recycle system (diluentrecycling system) or Controlling System or combination for suitable reactor of the present invention.This type of reactor can comprise continuous wave output (take-off) and the directly recirculation of catalyzer, thinner and polymkeric substance.Generally speaking, continuous process can comprise and continuously by monomer, catalyzer and thinner, introduces in polymerization reactor and remove continuously the suspension that contains polymer beads and thinner from this reactor.
Polymerization reactor system of the present invention can comprise the reactor of one type of a system or comprise the multiple reactor system, and it comprises the reactor of two or more types of parallel or serial operation.The multiple reactor system can comprise linking together carries out the reactor of polymerization, or the reactor do not connected.Polymkeric substance can polymerization in a reactor under a set condition, and then polymkeric substance can be transferred in the second reactor and carry out polymerization under different set conditions.
In one aspect of the invention, the polymerization reactor system can comprise at least one loop slurry reactor (loop slurry reactor).This type of reactor is well known in the art, and can comprise vertical or horizontal loop.This type of loop can comprise single loop or serial loop.The multiloop reactor can comprise vertical and horizontal loop.Slurry polymerization can carry out in organic solvent, and described organic solvent can dispersed catalyst and polymkeric substance.The example of suitable solvent comprises butane, hexane, hexanaphthene, octane and Trimethylmethane.Monomer, solvent, catalyzer and any comonomer are continuously fed in loop reactor, and polymerization occurs there.Polymerization can occur under low temperature and low pressure.Reactor effluent can be flashed, to remove solid resin.
In another aspect of the present invention, polymerization reactor can comprise at least one Gas-phase reactor.This type of system can be used continuous cycling stream under catalyzer exists under polymerizing condition, and this cycling stream contains one or more monomers, cycles through continuously fluidized-bed.This cycling stream can be regained from fluidized-bed, and recirculation turns back in reactor.Simultaneously, polymer product can take out from reactor, and new or fresh monomer can be added into to replace the monomer be aggregated.This type of Gas-phase reactor can comprise the process of the multistep vapour phase polymerization of alkene, and wherein alkene independently is aggregated with gas phase in the vapour phase polymerization district at least two, will in the first polymeric area, be added in the second polymeric area by the formed polymkeric substance containing catalyzer simultaneously.
In another aspect of the present invention, polymerization reactor can comprise tubular reactor (tubularreactor).Tubular reactor can cause or by using the catalyzer that generally is used to polycoordination to prepare polymkeric substance by free radical.Tubular reactor can have several districts, and fresh monomer, initiator or catalyzer are added into there.Monomer is carried in inert gas, and is introduced in reactor Yi Ge district.Initiator, catalyzer and/or catalyst component can be carried in air-flow, and are introduced in another district of reactor.Air-flow is mixed to carry out polymerization.Can suitably utilize heat and pressure, to obtain best polymeric reaction condition.
In another aspect of the present invention, polymerization reactor can comprise solution polymerization reactor.In the process of solution polymerization, by suitable stirring or other method, monomer contacts with catalyst composition.Can use the carrier that comprises inertia organic thinner or excess monomer.If necessary, in the situation that exist or lack liquid substance, can make monomer contact with catalytic reaction products with gas phase.Polymeric area is maintained under the temperature and pressure that the solution that will cause polymkeric substance forms in reaction medium.Can use stirring between polymerization period, control to obtain better temperature, and maintain uniform polyblend at whole polymeric area.Suitable method is used to disperse the heat release of polymerization.Can or realize in a continuous manner polymerization in mode in batches.Reactor can comprise a series of at least one separator, and it separates the polymkeric substance of expectation with low pressure with high pressure.
Of the present invention other aspect, the polymerization reactor system can comprise the combination of two or more reactors.In multiple reactor, the production of polymkeric substance can be included at least two several stages in polymerization reactor independently, described at least two independently polymerization reactor by transfer equipment, interconnect, this makes the polymkeric substance that will be produced by the first polymerization reactor be transferred to the second reactor is possible.Expectation polymerizing condition in one of reactor can be different from the operational condition of other reactor.Alternatively, the polymerization in multiple reactor can comprise that polymkeric substance is from a reactor manual transfer to reactor subsequently, to carry out continuous polymerization.Such reactor can comprise any combination, and it includes but not limited to combination, autoclave reactor (autoclave reactors) or the combination of solution reactor and gas phase or loop reactor, many solution reactors or many autoclave reactors of multiloop reactor, many Gas-phase reactor, loop and Gas-phase reactor.
In another aspect of this invention, can prepare with several different methods by catalyzer, include but not limited to, by catalyst component, directly feeds in polymerization reactor continuously, the pre-contact procedure that comprises some or all optional catalyst components, before this step occurs in they is introduced to reactor.In this respect, each optional pre-contact procedure can comprise the time that pre-contact is different.In this respect, present invention resides in initiated polymerization many, the optional pre-contact procedure of a plurality of time length before.In addition, these many, optional pre-contact procedures can be at least one pre-contacting container will contact in advance component introduce reactor in before occur, they can occur in polymerization reactor itself, or their arbitrary combination, comprise and use the how pre-contacting container that comprises the different catalysts component.Therefore, at this aspect, any pre-contact procedure can comprise any combination of pre-contact catalyst component, comprises any optional catalyst component.Equally in this respect, this many, optional pre-contact procedure can comprise different pre-duration of contacts.
In another aspect of this invention, can be by catalyst component being sent into continuously in any amount of optional pre-contacting container and subsequently this component being introduced continuously in reactor and Kaolinite Preparation of Catalyst.On the one hand, for example, the invention provides the method that produces catalyst composition, comprising:
Make at least one metallocene, at least one organo-aluminium compound and at least one alkene or alkynes contact first paragraph time, with formation, comprise that at least one contacts metallocene in advance, at least one contacts the pre-contact mixture of organo-aluminium compound and at least one pre-contact alkene or alkynes in advance; With
Make pre-contact mixture contact the second segment time with at least one acidic activator-carrier, with formation, comprise at least one rear metallocene, at least one rear contact organo-aluminium compound, at least one rear rear rear contact mixture that contacts acidic activator-carrier of alkene or alkynes and at least one that contacts of contacting.
On the other hand, for example, the invention provides the method that produces catalyst composition, comprising:
Make at least two kinds of catalyst component, at least one organo-aluminium compound, at least one alkene or alkynes or at least one acidic activator-carrier contact first paragraph times that comprise at least one metallocene, the pre-contact mixture that contains pre-contact catalyst component with formation; With
This pre-contact mixture is contacted with any catalyst component that is not used to form this pre-contact mixture, and optionally make this pre-contact mixture contact the second segment time with the other catalyst component that contains at least one metallocene, at least one organo-aluminium compound, at least one alkene or alkynes or at least one acidic activator-carrier, to form rear contact mixture, it contacts metallocene after comprising at least one, contact organo-aluminium compound, at least one rear contact alkene or alkynes and at least one rear contact acidic activator-carrier after at least one.
On the other hand, each composition can be admitted to reactor, or directly is admitted to, or by least one pre-contacting container, uses known charging, measurement and operating device for example pump, quality and volumetric flow meter and controller and analogue and be admitted to.Feedback signal can form and introduce together with this continuous catalyst with control loop (control loops) and be used.Mass flowmeter can be the Coriolis-type meter, and it is suitable for measuring for example flowing from the positive displacement pump with 3 pressure heads (positive displacement pumpwith three heads) of multiple types of flow.The combination of the pump of other type, instrument and similar type equipment can be used as the method for feed and control, to measure and to control the delivery rate of catalyst component.According to amount and the flow velocity of the expectation of the chemical compatibility of the type of component, component and component, the multiple combination of the method for feed and control also can be for other component of each minute, and as well known to those of ordinary skill in the art.For example, suited instrumentation for feed and control method can be, but be not limited to, thermal mass flow sensors (thermal mass flow meter), volumetric flow meter be cellular type (orifice-type), membrane type (diaphragm-type), water level formula (level-type) meter for example, or analogue.
On the other hand, before being introduced into polymerization reactor, catalyst component can be combined with multiple or different order and combination.On the one hand, for example, make metallocene contact the first paragraph pre-contact time with alkene in advance with aluminum alkyls in the first pre-contacting container, for example can reach 7-10 days, to form the first pre-contact solution.Then, send in the second pre-contacting container lasting second segment pre-contact time together with the soild oxide component of this first pre-contact solution and processing and optional more aluminum alkyls.In this respect, for example, the second pre-contact time can be shorter, longer or identical with the first pre-contact time.For example, the second pre-contact time can be 0.5 hour, and " rear contact " mixture can directly be admitted to reactor itself from the second pre-contacting container afterwards.In another aspect of this invention, before being introduced directly into reactor, all catalyst components can be brought in pre-contacting container together, continue the first paragraph time.
On the other hand, the part of each catalyst component can directly be sent in reactor, and remaining part is admitted in pre-contacting container simultaneously.In this respect, for example, sometimes the soild oxide of expectation restriction metallocene or processing is exposed to aluminum alkyls, in this case, only a small amount of aluminum alkyls is introduced in pre-contacting container, perhaps be introduced separately into, or introduce from the solution that also comprises alkene and metallocene, and the remainder of aluminum alkyls can be introduced directly into reactor.Similarly, as the part of catalyzer prepared product and the amount of the alkene of feed can be from the multi-source feed.For example, can in the first contact procedure, the 1-hexene be added in metallocene solution, to form the first pre-contact solution, in the second pre-contact procedure, more 1-hexene is added separately to this metallocene solution, to form the second pre-contact solution, and more the 1-hexene directly adds reactor.Similarly, any other catalyst component also can be added into whole reactor system in multi-step.
After polymkeric substance produces, they can be formed various goods, include but not limited to household receptacle, utensil, film product, drum, fuel tank, pipe, geomembrane (geomembranes) and lining (liners).The whole bag of tricks can form these goods.In one aspect, additive and properties-correcting agent be introduced in polymkeric substance, and purpose is to provide the effect of special expectation.
Definition
In order more clearly to be defined in term used herein, the definition below providing.When the definition provided when any file be introduced in this article as a reference or usage are conflicted mutually with definition mentioned herein or usage, follow definition mentioned herein or usage.
The multipolymer of homopolymer, ethene and another olefin comonomer that term polymer (polymer) is used to refer to contain ethene at this or their arbitrary combination.Term polymer also is used in reference to homopolymer and the multipolymer of acetylene at this.
Term promotor (cocatalyst) is used herein at least one organo-aluminium compound that refers to form the catalyst mixture component.Typical promotor is trialkyl aluminium compound, dialkyl aluminum halide compound and alkyllithium dihalide compound.Can use the term promotor, and no matter the real function of compound or any chemism that compound can work.
Term inert atmosphere (inert atmosphere) is used herein to and refers to that the material surround or cover for specific reaction, process or ambiance is the ambiance of non-reacted any type substantially.Therefore, this term is normally used for referring to when reacting or any parent, component, intermediate or the product of process basic anaerobic and without the use of the blanketing gas of moisture during for specific gas or moisture-sensitive, include but not limited to dry argon, dry nitrogen, the helium of drying or their mixture.In addition, rare gas element also be used in reference to when reaction or any parent, component, intermediate or the product of process only for moisture-sensitive and when insensitive to oxygen dry air as the use that covers atmosphere.Yet inert atmosphere will be got rid of CO usually as used herein 2or CO, because being expected the material that for specific reaction, process or they, will surround or cover, these gases there is reactivity, although they are used as the inertia blanketing gas once in a while in other process.
The pre-contact mixture of term (precontacted mixture) is used to describe the first mixture of catalyst component at this, be used to form the rear contact mixture or the second mixture of catalyst component at described the first mixture before, this first mixture is touched the first paragraph time, and the rear contact mixture of described catalyst component or the second mixture are contacted the second segment time in advance.In one aspect of the invention, pre-contact mixture has been described the mixture of metallocene, alkene or alkyne monomer and organo-aluminium compound, then this mixture and acidic activator-carrier with optionally with organo-aluminium compound, contact.Therefore, the component that is used to be in contact with one another has been described in pre-contact, but this contact is to carry out before the component with second, in rear contact mixture contacts.Therefore, the present invention can distinguish this component after being produced for the preparation of the component of pre-contact mixture and this mixture sometimes.For example, according to this specification sheets, once, after the organo-aluminium compound of pre-contact and metallocene and alkene or alkyne monomer are mixed, it may react and form at least one compound, composition (formulation) or the structure different from the different organo-aluminium compounds that are used to prepare pre-contact mixture.In this case, contact in advance organo-aluminium compound or component and be described to comprise the organo-aluminium compound that is used to prepare pre-contact mixture.
Equally, contact mixture after term (postcontacted mixture) is used to describe the second mixture of catalyst component at this, described catalyst component is touched the second segment time, and one of its composition is pre-contact mixture or the first mixture that is touched the catalyst component of first paragraph time.Usually, after term, contact mixture is used to describe the mixture of metallocene, alkene or alkyne monomer, organo-aluminium compound and acidic activator-carrier at this, and it is that pre-contact mixture by making these components of part contacts and forms with any other component that is added into to form rear contact mixture.Generally speaking, be added into and the other component that forms rear contact mixture is acidic activator-carrier, and optionally can include machine aluminium compound, it is identical or different from the organo-aluminium compound that is used to prepare pre-contact mixture, as said.Therefore, the present invention also can distinguish the component that is used to prepare rear contact mixture and mixture this component after being produced sometimes.
The term metallocene is used to refer to contain at least one η at this 5the metallocene of-alkadienyl part and metallocene similar compound, on the one hand, be used in reference to and contain at least one η 5the metallocene of-cycloalkadienyl part and metallocene similar compound, and be used in reference on the other hand and contain at least one η 5-cyclopentadienyl ligands, or the metallocene of its analogue or derivative and metallocene similar compound.Therefore, metallocene of the present invention generally includes at least one cyclopentadienyl, indenyl, fluorenyl or boron benzene part or their substitutive derivative.Possible substituting group on these parts comprises hydrogen, therefore, statement " their substitutive derivative (substitutedderivatives thereof) " comprises the part of fractional saturation, for example fluorenyl of the fractional saturation of the indenyl of the fractional saturation of the fluorenyl of the indenyl of tetrahydro indenyl, tetrahydrofluorenyl, octahydrofluorenyl, fractional saturation, fractional saturation, replacement, replacement and analogue in the present invention.In some contexts, metallocene is referred to simply as " catalyzer ", as term " promotor (cocatalyst) ", at this, is used to refer to organo-aluminium compound.
Term catalyst compositions (catalyst composition), catalyst mixture (catalystmixture) and similar terms this be used to or refer to pre-contact mixture or refer to after contact mixture, as the requirement of context institute.The use of these terms is not depended in the character at the actual product of these components of combination component of mixture reaction afterwards, active catalytic position or for the preparation of the course of aluminum cocatalyst, metallocene compound, alkene or the alkyne monomer of contact mixture or the concrete reaction of acidic activator-carrier in advance.Therefore, term catalyst compositions, catalyst mixture and similar terms comprise heterogeneous compositions (heterogeneouscompositions) and homogeneous composition (homogenous compositions).
Term alkyl (hydrocarbyl) is used to refer to the hydrocarbon free radical at this, it includes but not limited to aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl group, cycloalkadienyl, alkynyl, aralkyl, arylalkenyl (aralkenyl), sweet-smelling alkynyl (aralkynyl) and analogue, and comprises derivative its all replacements, that unsubstituted, side chain, straight chain, heteroatoms replace.
Term solid acid activator-carrier, acidic activator-carrier or be only that activator-carrier and analogue are used to indicate the solid inorganic oxide of the processing of relative high porosity at this, its performance lewis acidity or Bronsted acidity character, and it is generally anionic treatments by the electrophilic component, and it is calcined.The electrophilic component is generally electrophilic negative ion source compound.Therefore, on the one hand, the solid oxidation compounds of processing comprises the calcining product of contact of at least one solid oxidation compounds and at least one electrophilic negative ion source compound.On the other hand, activator-carrier or " the solid oxidation compounds of processing " comprise at least one ionizing acidic solid oxide compound.Term carrier or activator-carrier are not used to imply that these components are inertia, and this component should not be considered to the inert component of catalyst composition.
Although similar or be equivalent to those any method, equipment and material described herein and can be used in practice of the present invention or test, general method, equipment and material are described at this.
All publications described herein and patent are incorporated herein by reference, and purpose is to describe and open structure and the methodology for example be described in described publication, and it may be used in conjunction with current described invention.Publication discussed above and that run through in full is provided, only because they are open before the applying date of the present invention.Nothing can be interpreted as admitting herein: because these are formerly invented, the contriver haves no right to take the lead in these open source literatures.
For any particular compound disclosed herein, the general structure presented also comprises all conformers, positional isomers (regioisomers) and steric isomer, and they can produce from concrete substituting group group.Described general structure also comprises all enantiomorphs, diastereomer and no matter is other optically active isomer in enantiomeric form or racemic form, and the mixture of steric isomer, as required as context.
The present invention is further explained by the following examples, and described embodiment is interpreted as its scope is limited never in any form.On the contrary, it should be clearly understood that, can rely on various other sides, embodiment, modification and its Equivalent, after the specification sheets of reading this paper, it can make those of ordinary skills and expect them in the situation that do not deviate from the scope of spirit of the present invention or appended claims.
Below in embodiment, unless otherwise prescribed, synthetic and preparation described herein is carried out under as nitrogen or argon at inert atmosphere.Solvent is purchased from commercial source, and generally before use through the activated alumina drying.Unless otherwise prescribed, reagent obtains from commercial source.
Embodiment 1
The preparation of fluorinated silica-aluminum oxide acidic activator-carrier
Silica-alumina for the preparation of the fluorinated silica in the present embodiment-aluminum oxide acidic activator-carrier obtains with Grade MS13-110 from W.R.Grace, and it contains 13% aluminum oxide, has pore volume and the 400m of 1.2cc/g 2the surface-area of/g.This material is preliminary moistening being fluorinated by the solution impregnation with fluorinated hydrogen ammonium, and the amount of described solution is enough to equal the 10wt% of silica-alumina weight.Then by this impregnation of matters in vacuum drying oven under 100 ℃ dry 8 hours.Fluorinated silica-the alumina sample that then will obtain in this kind of mode is calcined as follows.10 gram aluminum oxide are placed on to 1.75 inches to be equipped with in the silica tube of sintered quartz dish in bottom.When silicon-dioxide by rest on dish the time, dry air with 1.6 to 1.8 standard cubic foots/hour linear rate upwards blow over dish.The speed that electric furnace around silica tube is used to 400 ℃/hs increases to the temperature of pipe the outlet temperature of 450 ℃.At this temperature, silica-alumina is fluoridized three hours in dry air.Afterwards, collect silica-alumina and also be stored under drying nitrogen, and in the situation that be not exposed to atmosphere and use.
Embodiment 2
The preparation of pre-contact/rear contact catalyst composition with and the comparison of polymerization activity and standard catalyst composition
Test the present invention in the comparative studies of catalyst composition of the pre-contact procedure that has and do not have metallocene, TEA and 1-hexene, affiliated catalyst composition comprises two (cyclopentadienyl) zirconium dichloride catalyzer, triethyl aluminum (TEA), monomer (ethene) and comonomer (1-hexene) and acidic activator-carrier (fluorinated silica-aluminum oxide).In this research, resulting data are provided in table 1, use the acidic activator-carrier of fluorinated silica-aluminum oxide.
Preparation is in the 45mL drying, two (cyclopentadienyl) zirconium dichloride storage liquid of 45mg in degassed toluene, for the test of table 1.The polyreaction data that the comparative examples 2A of table 1 means from almost making 5mL two (cyclopentadienyl) zirconium dichloride storage liquid, 200mg fluorinated silica aluminum oxide, the triethyl aluminums (TEA) of the 15wt% of 1mL in heptane simultaneously, 20g comonomer (1-hexene) contacts with monomer (ethene) and obtain, there is not the pre-contact (extended precontacting) of the extension of any catalyst component in it.
Carry out as follows polyreaction in 1 gallon of (3.785 L) autoclave.Purge under (purge) two (cyclopentadienyl) zirconium dichloride storage liquid of 5mL are fed to autoclave at Trimethylmethane, afterwards charging 200mg carrier-activator at once.Sealing autoclave, add the triethyl aluminum (TEA) of 2 liters of Trimethylmethanes 15wt% in heptane together with 20g 1-hexene and 1mL.When the time durations at 2 minutes is heated to 90 ℃ by reactor, start to stir and remain on 700rpm.With ethene, make total pressure reach 550psig (3890kPa).When needed ethene is sent in reactor, pressure is remained on to 550psig (3890kPa).After 1 hour, then stop agitator and heating and make the reactor reduction of blood pressure in high-speed.Then, open autoclave physics and take out solid polyethylene.The activity value provided in the embodiment 2A of table 1 provides for catalyzer relatively and the baseline of activator activity.
The embodiment 2B of table 1 confirms, before being fed to autoclave, makes two (cyclopentadienyl) zirconium dichlorides contact in advance and obtain having than the more highly active catalyzer of the catalyzer of embodiment 2A with TEA with the 1-hexene.Therefore, process 5mL metallocene storage liquid with the triethyl aluminum of 2mL 1-hexene and the 15wt% of 1mL in heptane.Before being fed to autoclave, this solution is stirred 30 minutes.Then, this contacts in advance solution and is fed to 1 gallon of (3.785L) autoclave, afterwards charging 200mg activator-carrier at once.Then, sealing autoclave 2L Trimethylmethane and 20g 1-hexene are added in reactor rapidly.When the time durations at 2 minutes is heated to 90 ℃ by reactor, start to stir and remain on 700rpm.With ethene, make total pressure reach 550psig (3890kPa).When needed ethene is sent in reactor, pressure is remained on to 550psig (3890kPa).After 53 minutes, then stop agitator and heating and make the reactor reduction of blood pressure in high-speed.Then, open autoclave physics and take out solid polyethylene.Reactor is substantially without any the sign of the dirt of wall dirt (wall scale), coat or other form.
Figure G05825926520070201D000431
Figure G05825926520070201D000432
Embodiment 3
By the polymerization activity that changes the catalyst composition prepared with the rear component contacted by pre-contact, compare
In the embodiment 3A-3D described in table 2, with multiple combination, by the toluene storage liquid of two (cyclopentadienyl) zirconium dichlorides of triethyl aluminum, 2mL 1-hexene and the 200mg fluorinated silica of 1mL 15wt.%-aluminum oxide activating agent-carrier optionally treating 1mL 1 mg/1mL 30 minutes, then this mixture is introduced to the polymerization pressure kettle.Prepare described storage liquid by dissolving two (cyclopentadienyl) zirconium dichlorides of 45mg in the toluene in the 45mL drying under nitrogen atmosphere.Carry out polyreaction 60 minutes with 20 gram 1-hexenes under 90 ℃, the ethene of 550psig (3890kPa) in Trimethylmethane."Yes" or "No" in table 2 means respectively the existence in pre-contact mixture or do not exist in introducing the autoclave time durations of first 30 minutes of these reactants.
In embodiment 3A, the toluene storage liquid of processing two (cyclopentadienyl) zirconium dichlorides of 1mL 1mg/1mL with trialkylaluminium and the 2mL 1-hexene of the 15wt.% of 1mL in heptane under nitrogen atmosphere.Before being fed to autoclave, this pre-contact mixture composition that contains these three kinds of reactants is stirred 30 minutes.Then, this contacts in advance solution and is fed to 1 gallon of (3.785L) autoclave, afterwards charging 200mg activator-carrier at once.Then, sealing autoclave 2L Trimethylmethane and 20g 1-hexene are added in reactor rapidly.When the time durations at 2 minutes is heated to 90 ℃ by reactor, start to stir and remain on 700rpm.With ethene, make total pressure reach 550psig (3890kPa).Therefore, the rear solution that contacts that contains pre-contact solution and carrier activator is allowed to keep in touch the time durations of 2 minutes before introducing ethene.When needed ethene is sent in reactor, pressure is remained on to 550psig (3890kPa).After 60 minutes, then stop agitator and heating and make the reactor reduction of blood pressure in high-speed.Then, open autoclave physics and take out solid polyethylene.Reactor is substantially without any the sign of the dirt of wall dirt (wall scale), coat or other form.
In embodiment 3B, only with the triethyl aluminum of 1mL 15wt.%, process the toluene storage liquid of two (cyclopentadienyl) zirconium dichlorides of 1mL 1mg/1mL in pre-contact mixture.Before being fed to autoclave, this pre-contact mixture composition that contains these two kinds of reactants is stirred 30 minutes.Then, this contacts in advance solution and is fed to 1 gallon of (3.785L) autoclave, afterwards charging 200mg activator-carrier at once.Then, sealing autoclave 2L Trimethylmethane and 20g 1-hexene are added in reactor rapidly.When the time durations at 2 minutes is heated to 90 ℃ by reactor, start to stir and remain on 700rpm.With ethene, make total pressure reach 550psig (3890kPa).Therefore, the rear solution that contacts that contains pre-contact solution and carrier activator is allowed to keep in touch the time durations of 2 minutes before introducing ethene.When needed ethene is sent in reactor, pressure is remained on to 550psig (3890kPa).After 60 minutes, then stop agitator and heating and make the reactor reduction of blood pressure in high-speed.Then, open autoclave physics and take out solid polyethylene.Reactor is substantially without any the sign of the dirt of wall dirt (wallscale), coat or other form.The present embodiment obtains the activity lower than embodiment 3A.
In embodiment 3C, only with 2mL 1-hexene, process the toluene storage liquid of two (cyclopentadienyl) zirconium dichlorides of 1mL 1mg/1mL in pre-contact mixture.Before being fed to autoclave, this pre-contact mixture composition that contains these two kinds of reactants is stirred 30 minutes.Then, this contacts in advance solution and is fed to 1 gallon of (3.785L) autoclave, afterwards charging 200mg activator-carrier at once.Then, sealing autoclave the triethyl aluminum together with 20g 1-hexene and 1mL 15wt.% adds in reactor rapidly by the 2L Trimethylmethane.When the time durations at 2 minutes is heated to 90 ℃ by reactor, start to stir and remain on 700rpm.With ethene, make total pressure reach 550psig (3890kPa).Therefore, the rear solution that contacts that contains pre-contact solution and carrier activator is allowed to keep in touch the time durations of 2 minutes before introducing ethene.When needed ethene is sent in reactor, pressure is remained on to 550psig (3890kPa).After 60 minutes, then stop agitator and heating and make the reactor reduction of blood pressure in high-speed.Then, open autoclave physics and take out solid polyethylene.Reactor is substantially without any the sign of the dirt of wall dirt (wall scale), coat or other form.The present embodiment obtains the activity lower than embodiment 3A.
In embodiment 3D, use the toluene storage liquid of 2mL 1-hexene and two (cyclopentadienyl) zirconium dichlorides of 200mg activator-vehicle treated 1mL 1mg/1mL in pre-contact mixture.Before being fed to autoclave, this pre-contact mixture composition that contains these three kinds of reactants is stirred 30 minutes.Then, this contacts in advance slurries and is fed to 1 gallon of (3.785L) autoclave, afterwards charging 200mg activator-carrier at once.Then, sealing autoclave the triethyl aluminum together with 20g 1-hexene and 1mL 15wt.% adds in reactor rapidly by the 2L Trimethylmethane.When the time durations at 2 minutes is heated to 90 ℃ by reactor, start to stir and remain on 700rpm.With ethene, make total pressure reach 550psig (3890kPa).Therefore, the rear solution that contacts that contains pre-contact solution and carrier activator is allowed to keep in touch the time durations of 2 minutes before introducing ethene.When needed ethene is sent in reactor, pressure is remained on to 550psig (3890kPa).After 60 minutes, then stop agitator and heating and make the reactor reduction of blood pressure in high-speed.Then, open autoclave physics and take out solid polyethylene.Reactor is substantially without any the sign of the dirt of wall dirt (wall scale), coat or other form.The present embodiment obtains the activity lower than embodiment 3A.
Figure G05825926520070201D000451
These tests have confirmed in the situation that do not exist activator-carrier pre-contact metallocene and 1-hexene and TEA to have higher activity.
Embodiment 4
Be derived from catalyzer active of different pre-contacts and rear contact catalyst composition and the research that has activator-carrier in contact catalyst composition in advance
The test 4A described in table 3 and 4B provide and have contained metallocene catalyst, two (2,7-di-t-butyl fluorenyl)-ethyl-1, the comparison of the catalyst composition of 2-bis-base zirconium dichlorides (IV), triethyl aluminum (TEA), monomer (ethene) and comonomer (1-hexene) and fluorinated silica-aluminum oxide activating agent-carrier.According to the data in table 3, before being introduced into the polyreaction autoclave, triethyl aluminum, 2mL 1-hexene and the 200 mg fluorinated silica of use 1mL 15wt.%-aluminum oxide activating agent-carrier optionally treating 1mg metallocene/1mL toluene storage liquid (6mL) 45 minutes.Therefore, the "Yes" or "No" table of articles in table 3 is shown in the existence of these reactants before pre-contact mixture is introduced to autoclave in 45 minutes pre-contact procedures with metallocene.Carry out polyreaction 60 minutes with 20 gram 1-hexenes under 80 ℃, the ethene of 450psig (3200kPa) in Trimethylmethane.
In embodiment 4A, under nitrogen atmosphere, use the trialkylaluminium of the 15wt.% of 1mL in celebrating alkane and 2mL 1-hexene to process two (2,7-di-t-butyl fluorenyl)-ethyl-1 of 6mL 1mg/1mL, the toluene storage liquid of 2-bis-base zirconium dichlorides (IV).Before being fed to autoclave, this pre-contact mixture composition that contains these three kinds of reactants is stirred 45 minutes.Then, this contacts in advance solution and is fed to 1 gallon of (3.785L) autoclave, afterwards charging 200mg activator-carrier at once.Then, sealing autoclave 2 L Trimethylmethanes and 20g 1-hexene are added in reactor rapidly.When the time durations at 2 minutes is heated to 80 ℃ by reactor, start to stir and remain on 700rpm.With ethene, make total pressure reach 450psig (3200kPa).Therefore, the rear solution that contacts that contains pre-contact solution and carrier activator is allowed to keep in touch the time durations of 2 minutes before introducing ethene.When needed ethene is sent in reactor, pressure is remained on to 450psig (3200kPa).After 60 minutes, then stop agitator and heating and make the reactor reduction of blood pressure in high-speed.Then, open autoclave physics and take out solid polyethylene.
Figure G05825926520070201D000461
In comparing embodiment 4B, fluorinated silica-aluminum oxide activating agent-carrier and two (2,7-di-t-butyl fluorenyl)-ethyl-1,2-bis-base zirconium dichloride (IV) metallocene catalysts, triethyl aluminum (TEA) and hexane comonomer are present in pre-contact mixture together.Therefore, the toluene storage liquid of trialkylaluminium, 2mL1-hexene and the 200mg activator of the 15wt.% of use 1mL in heptane-carrier pulp 6mL 1mg/1mL metallocene.Before being fed to autoclave, this pre-contact mixture composition that contains all four kinds of catalyst components is stirred 45 minutes.Then, sealing autoclave 2 L Trimethylmethanes and 20g 1-hexene are added in reactor rapidly.When the time durations at 2 minutes is heated to 80 ℃ by reactor, start to stir and remain on 700rpm.With ethene, make total pressure reach 450psig (3200kPa).When needed ethene is sent in reactor, pressure is remained on to 450psig (3200kPa).After 60 minutes, then stop agitator and heating and make the reactor reduction of blood pressure in high-speed.Then, open autoclave physics and take out solid polyethylene.As shown in table 3, embodiment 4B catalyzer shows than the lower catalyst activity of embodiment 4A catalyzer.
Embodiment 5
The preparation of multiple pre-contact and rear contact catalyst composition and the comparison of their polymerization activity
Being presented on test in table 4 provides the comparison of catalyst composition, and described catalyst composition comprises metallocene catalyst [η 5-cyclopentadienyl-η 5-(9-fluorenyl) oneself-1-alkene] zirconium dichloride CH 2=CHCH 2cH 2c (CH 3) (Cp) (9-Flu) ZrCl 2, triethyl aluminum (TEA), monomer (ethene) and comonomer (1-hexene) and fluorinated silica-aluminum oxide activating agent-carrier, it has or does not have the pre-contact procedure of metallocene, TEA and 1-hexene.Metallocene catalyst [(η in the present embodiment 5-C 5h 4) CCH 3(CH 2cH 2cH=CH 2)-(η 5-9-C 13h 9)] ZrCl 2there is following structure:
Wherein R1 is methyl, and R2 is butenyl (CH 2cH 2cH=CH 2), and R3 is H.
Embodiment 5A represents the standard catalytic test, and it obtains as follows.Under nitrogen atmosphere, by 2mL 1-hexene, by [the η in toluene (2mg/mL) 5-cyclopentadienyl-η 5-(9-fluorenyl) oneself-1-alkene] zirconium dichloride CH 2=CHCH 2cH 2c (CH 3) (Cp) (9-Flu) ZrCl 22mL solution and the 15wt.% triethyl aluminum of 1mL in n-heptane solution of the catalyst solution of preparation add in the Diels-Alder pipe.This solution is added in 250mg activator-carrier at once.Therefore, the CH of the embodiment 5A of table 4 representative from almost contact simultaneously 2=CHCH 2cH 2c (CH 3) (Cp) (9-Flu) ZrCl 2, TEA, 1-hexene and fluorinated silica-aluminum oxide activating agent-carrier and the polyreaction data that obtain, therefore and do not make ansa-metallocene, triethyl aluminum (TEA) contact in advance with the 1-hexene, and provide the baseline for comparing with embodiment 5B and 5C.
Embodiment 5B representative is identical mode and the catalytic test that obtains according to the standard test with embodiment 5A, and just embodiment 5B comprises the metallocene CH of 0.25 hour 2=CHCH 2cH 2c (CH 3) (Cp) (9-Flu) ZrCl 2, TEA and 1-hexene pre-contact procedure, make afterwards this mixture contact with fluorinated silica-aluminum oxide activating agent-carrier.
Embodiment 5C representative is identical mode and the catalytic test that obtains according to the standard test with embodiment 5A, just embodiment 5C does not comprise that metallocene, TEA and the pre-of 1-hexene contact, and change " rear contact " step (according to the definition of this paper) that comprises 0.50 hour into, in this rear contact procedure, all components, i.e. metallocene CH 2=CHCH 2cH 2c (CH 3) (Cp) (9-Flu) ZrCl 2, TEA, 1-hexene and fluorinated silica-aluminum oxide activating agent-carrier should after contact mixture contacted before adding reactor.This embodiment proves, by pre-contact metallocene, TEA and 1-hexene, has obtained active increase, and contacts all reactants before starting polymerization, observes active reduction.
Embodiment 5D is prepared as follows.By metallocene catalyst CH 2=CHCH 2cH 2c (CH 3) (Cp) (9-Flu) ZrCl 2(24mg) be placed in the Diels-Alder pipe, and remain on dark state by cover this pipe with aluminium foil.Add the sample (but without hexene) of the dry heptane of 12-mL, and stir this mixture, add the 15wt.% triethyl aluminum of 2mL in heptane simultaneously.These slurries are at room temperature stirred 17 hours in dark, so that pale yellow solution to be provided.This sample is kept in the dark, until use.Embodiment 5D comprises that the 2mL of 0.25 hour should contact " contacting afterwards " step of solution, 1mL 15wt.%TEA and fluorinated silica-aluminum oxide activating agent-carrier in advance, and it is added in reactor afterwards.Embodiment 5D provides the baseline of comparing embodiment 5E and 5F.
Embodiment 5E is prepared as follows.By metallocene catalyst CH 2=CHCH 2cH 2c (CH 3) (Cp) (9-Flu) ZrCl 2(24mg) be placed in the Diels-Alder pipe, and remain on dark state by cover this pipe with aluminium foil.Add 12-mL1-hexene sample, and stir this mixture, add the 15wt.% triethyl aluminum of 2mL in heptane simultaneously.These slurries are at room temperature stirred 17 hours in dark, and so that dark yellow solution to be provided, wherein all catalyzer dissolve.This sample is kept in the dark, until use.This embodiment comprises " contacting afterwards " step of this solution of 2mL, 1mL 15wt.%TEA and the fluorinated silica-aluminum oxide activating agent-carrier of 0.25 hour, and it is added in reactor afterwards.
Embodiment 5F is prepared as follows.By CH 2=CHCH 2cH 2c (CH 3) (Cp) (9-Flu) ZrCl 2metallocene catalyst (10mg) is placed in the Diels-Alder pipe, adds wherein 20mL 1-hexene and the 2mL 15wt.% triethyl aluminum in heptane.This mixture is held in the dark, and the Diels-Alder pipe is placed in ultra sonic bath, and sonication 10 minutes.Obtain dark yellow solution, wherein all catalyzer dissolve.This sample is kept in the dark, until use.This embodiment comprises " contacting afterwards " step of this solution of 4mL, 1mL 15wt.%TEA and the fluorinated silica-aluminum oxide activating agent-carrier of 0.25 hour, and it is added in reactor afterwards.Embodiment 5E and 5F show, with the embodiment 5D that does not wherein comprise the 1-hexene, compare, and by making metallocene, TEA and 1-hexene, contact in advance, and activity is greatly enhanced.
Polyreaction is carried out as follows.After any pre-contact and rear contact procedure of specific sample, catalyst slurry (comprising metallocene, organoaluminum, alkene and activator-carrier) under purging, Trimethylmethane added to 1 gallon of (3.785L) autoclave.Sealing autoclave, add 2 liters of Trimethylmethanes, starts to stir and maintain under 700rpm.Be heated to rapidly 80 ℃ by reactor is during 2 minutes.25-g 1-hexene sample is pushed in reactor, with ethene, make total pressure reach 450psig (3200kPa).Ethene is sent in reactor when needed, so that pressure maintains 450psig (3200kPa) 1 hour.Then stop agitator and heating, and make the reactor rapid depressurization.Then open autoclave, and physics is removed solid polyethylene.
5D 17 4 0.25 4 60 0.0034 80.6 23706 23706 322
5E 17 5 0.25 60 0.0034 319.7 94029 94029 1279
5F 0.17 6 0.25 65 0.0018 294.7 151128 151128 1088
1pre-contact time is defined as metallocene CH 2=CHCH 2cH 2c (CH 3) (Cp) (9-Flu) ZrCl 2, triethyl aluminum (TEA) and 1-hexene duration of contact, they form pre-contact mixture.
2be defined as the duration of contact between all four components rear duration of contact, i.e. metallocene CH 2=CHCH 2cH 2c (CH 3) (Cp) (9-Flu) ZrCl 2, triethyl aluminum (TEA), 1-hexene and fluorinated silica-aluminum oxide activating agent-carrier.This also represents the duration of contact between pre-contact mixture and fluorinated silica-aluminum oxide activating agent-carrier.
3because polymerization velocity reduces at the end of test in 49 minutes, so per hour be extrapolated to the activity (g/g/hr) of baseline, form the too high estimation to activity.
4pre-contact and rear contact mixture be not containing any olefinic monomer.Therefore, pre-contact mixture contains metallocene CH 2=CHCH 2cH 2c (CH 3) (Cp) (9-Flu) ZrCl 2, triethyl aluminum (TEA) and heptane, but containing the 1-hexene.Rear contact mixture contains pre-contact mixture, other triethyl aluminum (TEA) and fluorinated silica-aluminum oxide.
5keep adusk pre-contact mixture.
6sonication and simultaneously keep adusk pre-contact mixture.
In table 4, productive rate (Productivity) is the polymkeric substance grams of producing in this process of the test/catalyzer grams, catalyst activity is polymkeric substance grams/catalyzer grams/unit time, and be the better comparison between test, and activator-carrier activity it is polymkeric substance grams/activator-carrier grams/unit time.
Embodiment 6
Use pre-contact/rear contact catalyst composition scale operation polyvinyl resin
In the present embodiment, pre-treatment metallocene catalyst of the present invention is used in the experimental production of polyvinyl resin of 0.931 density (specification limit is 0.930 to 0.933), to prove this catalyst system, produces the ability of polyethylene polymer with fairly large production.
In continuous particulate shape method (also referred to as slurry process) by make catalyzer and monomer and choose any one kind of them or more kinds of alpha-olefin comonomer for example the 1-hexene contact and prepare ethene polymers.Therefore select medium and temperature, make multipolymer produce as solid particulate and reclaim with this form.The ethene through activated alumina and/or molecular sieve drying is used as monomer.Degassed by classification and be used as thinner through the Trimethylmethane of aluminum oxide and/or molecular sieve drying.
Reactor is the 22.5-inch internal diameter tube loop that is full of liquid, has the volume of 27,000 gallons (102206.124L).Liquid isobutane is used as thinner, and reactor pressure is 600psig (4240kPa).Loop reactor is equipped with continuous wave output (continuous take-off, CTO) and sedimentation frame product output (PTO) (settling leg product take-off), its operation that can be combined.Come the polymkeric substance of autoreactor and Trimethylmethane to enter low pressure flash chamber together with the slurries discharging of unreacted ethene and 1-hexene by the flash lines (flashline) heated and by purge column (purge column) to remove residual hydrocarbon.For preventing the static accumulation in reactor, add the business static inhibitor of selling with Stadis 450 of (5ppm of<thinner) in a small amount.
Catalyst system comprises following component.Make two (indenyl) zirconium dichloride (η of metallocene in the first premix tank 5-C 9h 7) 2zrCl 2, 1-hexene thinner contacts 9 days in advance with triethyl aluminum (TEA), before this occurs in and is introduced into second " pre-mixing " container.After this time, form the metallocene-alkene of a charging-TEA mixture, form the activator-carrier of pulp in Trimethylmethane of the second charging and the other triethyl aluminum (TEA) in Trimethylmethane that forms the 3rd charging is introduced into second " pre-mixing " container, to form rear contact mixture, according to the present invention, before this occurs in and introduces loop reactor.Form rear contact mixture once be introduced into the second pre-mixing container, this mixture was stirred the approximately residence time of 28 minutes before being introduced into loop reactor.
Two (indenyl) zirconium dichloride concentration of metallocene is approximately 1 part of every 1,000,000 parts of reactor concentration.The total TEA added is approximately 10 parts of every 1,000,000 parts of reactor concentration.950 (510 ℃) are to 1000
Figure 10003_42
make the dehydration of solid activating agent-carrier under (537.8 ℃) in fluidized-bed, then be fed to for the conventional catalyst measuring container of chrome catalysts and by 35 or the feeder metering of 49-cc enter the second pre-mixing container.
The typical case of this test and approximate reactor condition are: 190
Figure 10003_43
the 1-hexene of the ethene of the temperature of reactor of (87.78 ℃), 5.5 to 7.0 weight percents by online gas chromatographic measurement in low pressure flash chamber tail gas, 3.5 to 4.5 weight percents by online gas chromatographic measurement in low pressure flash chamber tail gas, without hydrogen and reactor solids, can reach 38 weight percents.
The operant response device, to have residence time of 45 minutes to 1.5 hours.Under steady state conditions, isobutane feed speed is per hour 30,000 pound (13607.77kg) is to 36,000 pound (16329.33kg), ethylene feed speed for per hour 30,000 pounds (13607.77kg) to 34,000 pounds (15422.14kg), and 1-hexene input speed changes, to control the density of polymer product.Ethylene concentration in thinner is 5 to 7 weight percents.Catalyst concn in reactor can make in scope that the weight of catalyst system content based on reactor content is 0.001 to 1 weight percent.Polymkeric substance shifts out and reclaims in flashing chamber with the speed of 33,000 pounds (14968.55kg) to 37,000 pounds (16782.9kg) per hour from reactor.

Claims (31)

1. catalyst composition, comprising: at least one contacts metallocene in advance; At least one pre-contact organo-aluminium compound; At least one pre-contact alkene or alkynes; With after contact acidic activator-carrier,
Metallocene in wherein said pre-contact metallocene is the compound with following formula:
(X 1)(X 2)(X 3)(X 4)M 1，
M wherein 1titanium, zirconium or hafnium;
(X wherein 1) be independently the cyclopentadienyl of cyclopentadienyl, indenyl, fluorenyl, boron benzene, replacement, the indenyl of replacement, the fluorenyl of replacement or the boron benzene replaced;
Wherein at (X 1) the fluorenyl of indenyl, replacement of cyclopentadienyl, replacement of replacement or each substituting group on the boron benzene that replaces be independently combination, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative of aliphatic group, aryl, cyclic group, aliphatic group and cyclic group, any one in them has 1 to 20 carbon atom; Halogenide; Or hydrogen;
Wherein at (X 1) at least one substituting group optionally for connecting (X 1) and (X 2) bridging group;
(X wherein 3) and (X 4) be independently combination, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative of aliphatic group, aryl, cyclic group, aliphatic group and cyclic group, any one in them has 1 to 20 carbon atom; Or halogenide;
(X wherein 2) be independently combination, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative of cyclopentadienyl group, indenyl group, fluorenyl groups, boron phenyl group, aliphatic group, aryl, cyclic group, aliphatic group and cyclic group, any one in them has 1 to 20 carbon atom; Or halogenide;
(the X wherein replaced 2) on each substituting group be independently combination, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative of aliphatic group, aryl, cyclic group, aliphatic group and cyclic group, any one in them has 1 to 20 carbon atom; Halogenide; Or hydrogen; With
Wherein at (X 2) at least one substituting group optionally for connecting (X 1) and (X 2) bridging group;
Wherein said rear contact acidic activator-carrier is fluorinated silica-aluminum oxide;
The contact of wherein said at least one metallocene, at least one organo-aluminium compound and at least one alkene or alkynes continues the first paragraph time of 1 minute to 9 days to form pre-contact mixture; With
Described pre-contact mixture and the described fluorinated silica-aluminum oxide second segment time of lasting 1 minute to 24 hours that contacts is to form rear contact mixture.
2. the described catalyst composition of claim 1, the weight that wherein said fluorinated silica-aluminum oxide comprises the described fluorinated silica-aluminum oxide before calcining afterwards based on drying is 5% to 95% aluminum oxide and 2% to 50% fluoride ion by weight by weight.
3. the described catalyst composition of claim 1, the silica-alumina in wherein said fluorinated silica-aluminum oxide is that pore volume is that the above and surface-area of 0.5cc/g is 100m 2the silica-alumina that/g is above.
4. the described catalyst composition of claim 1, the metallocene in wherein said pre-contact metallocene is the metallocene compound that comprises following compounds:
Two (cyclopentadienyl) hafnium dichloride;
Two (cyclopentadienyl) zirconium dichloride;
Two (the η of 1,2-second, two bases 5-1-indenyl) two n-butoxy hafniums;
Two (the η of 1,2-second, two bases 5-1-indenyl) zirconium dimethyl;
Two (the η of 3,3-, penta 2 bases 5-4,5,6,7-tetrahydrochysene-1-indenyl) hafnium dichloride;
Two (the η of aminomethyl phenyl silyl 5-4,5,6,7-tetrahydrochysene-1-indenyl) zirconium dichloride;
Two (n-butyl cyclopentadienyl) two (tertiary fourth amino) hafnium;
Two (1-normal-butyl-3-methyl-cyclopentadienyl) zirconium dichloride;
Two (n-butyl cyclopentadienyl) zirconium dichloride;
Two (1-indenyl) zirconium dichlorides of dimetylsilyl;
Two (1-indenyl) hafnium dichloride of octyl group (phenyl) silyl;
Two (the η of dimetylsilyl 5-4,5,6,7-tetrahydrochysene-1-indenyl) zirconium dichloride;
Two (2-methyl isophthalic acid-indenyl) zirconium dichlorides of dimetylsilyl;
Two (9-fluorenyl) zirconium dichlorides of 1,2-second, two bases;
Indenyl diethoxy titanium chloride (IV);
(isopropylamino dimetylsilyl) CyclopentadienyltitaDichloride Dichloride;
Two (pentamethyl-cyclopentadienyl) zirconium dichloride;
Two (indenyl) zirconium dichloride;
Two (9-fluorenyl) zirconium dichlorides of methyl (octyl group) silyl;
Two (2,7-di-t-butyl fluorenyl)-ethyl-1,2-bis-base zirconium dichlorides (IV);
Two-[1-(N, N-diisopropylaminoethyl) boron benzene] hydrogenation trifluoromethane sulfonic acid zirconium;
Methyl-3-butenyl methylene radical (η 5-cyclopentadienyl) (η 5-9-fluorenyl) zirconium dichloride;
Methyl-3-butenyl methylene radical (η 5-cyclopentadienyl) (η 5-2,7-bis--tertiary butyl-9-fluorenyl) zirconium dichloride;
Methyl-4-pentenyl methylene radical (η 5-cyclopentadienyl) (η 5-9-fluorenyl) zirconium dichloride;
Methyl-4-pentenyl methylene radical (η 5-cyclopentadienyl) (η 5-2,7-bis--tertiary butyl-9-fluorenyl) zirconium dichloride;
Phenyl-3-butenyl methylene radical (η 5-cyclopentadienyl) (η 5-9-fluorenyl) zirconium dichloride;
Phenyl-3-butenyl methylene radical (η 5-cyclopentadienyl) (η 5-2,7-bis--tertiary butyl-9-fluorenyl) zirconium dichloride;
Phenyl-4-pentenyl methylene radical (η 5-cyclopentadienyl) (η 5-9-fluorenyl) zirconium dichloride; Or
Phenyl-4-pentenyl methylene radical (η 5-cyclopentadienyl) (η 5-2,7-bis--tertiary butyl-9-fluorenyl) zirconium dichloride.
5. the described catalyst composition of claim 1, the organoaluminum in wherein said pre-contact organo-aluminium compound is the organo-aluminium compound with following formula:
Al(X 5) n(X 6) 3-n，
(X wherein 5) be the alkyl with 2 to 20 carbon atoms; (X 6) be its any one there is alkoxide or aryl oxide, halogenide or the hydride of 1 to 20 carbon atom; With n be 1 to 3 number, 1 and 3 be also included within.
6. the described catalyst composition of claim 1, the organoaluminum in wherein said pre-contact organo-aluminium compound is triethyl aluminum (TEA), tri-propyl aluminum, diethyl aluminum ethylate, tri-butyl aluminum, diisobutylaluminium hydride, triisobutyl aluminium, diethylaluminum chloride or their combination.
7. the described catalyst composition of claim 1 also comprises that at least one has the rear contact organo-aluminium compound of following formula:
Al(X 5) n(X 6) 3-n，
(X wherein 5) be the alkyl with 1 to 20 carbon atom, (X 6) be any one alkoxide or aryl oxide, halogenide or hydride with 1 to 20 carbon atom; With n be 1 to 3 number, 1 and 3 be also included within.
8. the described catalyst composition of claim 1, the alkene in wherein said pre-contact alkene or alkynes or alkynes are that per molecule has 2 to 30 carbon atoms and has the compound of at least one carbon-to-carbon double bond or at least one carbon-to-carbon triple bond.
9. the described catalyst composition of claim 1, metallocene in wherein said pre-contact metallocene is two (indenyl) zirconium dichlorides, two (cyclopentadienyl) zirconium dichloride or two (2,7-di-t-butyl fluorenyl)-ethyl-1,2-bis-base zirconium dichlorides (IV); Described pre-contact organo-aluminium compound comprises triethyl aluminum; Described pre-contact alkene comprises the 1-hexene; And described rear contact acidic activator-carrier comprises fluorinated silica-aluminum oxide.
10. the described catalyst composition of claim 1, the organoaluminum in wherein said pre-contact organo-aluminium compound is aluminium pentamethylene, aluminium cyclopentadiene or aluminium cyclopentenes.
11. the described catalyst composition of claim 1, the mol ratio of wherein said metallocene and described organo-aluminium compound is 1: 1 to 1: 10,000.
12. the described catalyst composition of claim 1, wherein the mol ratio of alkene described in described pre-contact mixture or alkynes and described metallocene be 1: 10 to 100,000: 1.
13. the described catalyst composition of claim 1, the weight ratio of wherein said metallocene and described fluorinated silica-aluminum oxide is 1: 1 to 1: 1,000,000.
14. the described catalyst composition of claim 1, the weight ratio of wherein said fluorinated silica-aluminum oxide and described organo-aluminium compound is 1: 5 to 1000: 1.
15. the described catalyst composition of claim 1, the metallocene in wherein said pre-contact metallocene is the compound with formula I:
Wherein E is C, Si, Ge or Sn; R1 is H or the hydrocarbyl group with 1 to 12 carbon atom; R2 is the kiki alkenyl group with 3 to 12 carbon atoms; With R3 be H or the hydrocarbyl group with 1 to 12 carbon atom.
16. the described catalyst composition of claim 1, the metallocene in wherein said pre-contact metallocene is the compound with formula II:
Figure FFW00000049943000042
Wherein R1 is methyl or phenyl; R2 is 3-butenyl (CH 2cH 2cH=CH 2) or 4-pentenyl (CH 2cH 2cH 2cH=CH 2); With R3 be H or the tertiary butyl.
17. produce the method for catalyst composition, comprising:
Make at least one metallocene, at least one organo-aluminium compound and at least one alkene or alkynes contact first paragraph time, with formation, comprise that at least one contacts metallocene in advance, at least one contacts the pre-contact mixture of organo-aluminium compound and at least one pre-contact alkene or alkynes in advance; With
Make described pre-contact mixture contact the second segment time with acidic activator-carrier, with formation, comprise at least one rear metallocene, at least one rear contact organo-aluminium compound, at least one rear rear rear contact mixture that contacts acidic activator-carrier of alkene or alkynes and at least one that contacts of contacting; Wherein said acidic activator-carrier is fluorinated silica-aluminum oxide.
18. the described method of claim 17, wherein said metallocene, described organo-aluminium compound and described alkene or alkynes are contacted in advance the first paragraph time of 1 minute to 9 days in described pre-contact mixture.
19. the described method of claim 17, wherein said pre-contact mixture and described fluorinated silica-aluminum oxide are touched the second segment time of 1 minute to 24 hours in described rear contact mixture.
20. the described method of claim 17, the metallocene in wherein said pre-contact metallocene is the metallocene compound with following formula:
(X 1)(X 2)(X 3)(X 4)M 1，
M wherein 1titanium, zirconium or hafnium;
(X wherein 1) be independently the cyclopentadienyl of cyclopentadienyl, indenyl, fluorenyl, boron benzene, replacement, the indenyl of replacement, the fluorenyl of replacement or the boron benzene replaced;
Wherein at (X 1) the fluorenyl of indenyl, replacement of cyclopentadienyl, replacement of replacement or each substituting group on the boron benzene that replaces be independently combination, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative of aliphatic group, aryl, cyclic group, aliphatic group and cyclic group, any one in them has 1 to 20 carbon atom; Halogenide; Or hydrogen;
Wherein at (X 1) at least one substituting group optionally for connecting (X 1) and (X 2) bridging group;
(X wherein 3) and (X 4) be independently combination, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative of aliphatic group, aryl, cyclic group, aliphatic group and cyclic group, any one in them has 1 to 20 carbon atom; Or halogenide;
(X wherein 2) be independently combination, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative of cyclopentadienyl group, indenyl group, fluorenyl groups, boron phenyl group, aliphatic group, aryl, cyclic group, aliphatic group and cyclic group, any one in them has 1 to 20 carbon atom; Or halogenide;
(the X wherein replaced 2) on each substituting group be independently combination, oxygen groups, methylthio group, nitrogen groups, phosphorus group, arsyl group, carbon-based group, silicon group, germanium group, tin group, lead base group, boron group, aluminium base group, inorganic group, organometallic group or their substitutive derivative of aliphatic group, aryl, cyclic group, aliphatic group and cyclic group, any one in them has 1 to 20 carbon atom; Halogenide; Or hydrogen; With
Wherein at (X 2) at least one substituting group optionally for connecting (X 1) and (X 2) bridging group.
21. the described method of claim 17, the metallocene in wherein said pre-contact metallocene is the metallocene compound that comprises following compounds:
Two (cyclopentadienyl) hafnium dichloride;
Two (cyclopentadienyl) zirconium dichloride;
Two (the η of 1,2-second, two bases 5-1-indenyl) two n-butoxy hafniums;
Two (the η of 1,2-second, two bases 5-1-indenyl) zirconium dimethyl;
Two (the η of 3,3-, penta 2 bases 5-4,5,6,7-tetrahydrochysene-1-indenyl) hafnium dichloride;
Two (the η of aminomethyl phenyl silyl 5-4,5,6,7-tetrahydrochysene-1-indenyl) zirconium dichloride;
Two (n-butyl cyclopentadienyl) two (tertiary fourth amino) hafnium;
Two (1-normal-butyl-3-methyl-cyclopentadienyl) zirconium dichloride;
Two (n-butyl cyclopentadienyl) zirconium dichloride;
Two (1-indenyl) zirconium dichlorides of dimetylsilyl;
Two (1-indenyl) hafnium dichloride of octyl group (phenyl) silyl;
Two (the η of dimetylsilyl 5-4,5,6,7-tetrahydrochysene-1-indenyl) zirconium dichloride;
Two (2-methyl isophthalic acid-indenyl) zirconium dichlorides of dimetylsilyl;
Two (9-fluorenyl) zirconium dichlorides of 1,2-second, two bases;
Indenyl diethoxy titanium chloride (IV);
(isopropylamino dimetylsilyl) CyclopentadienyltitaDichloride Dichloride;
Two (pentamethyl-cyclopentadienyl) zirconium dichloride;
Two (indenyl) zirconium dichloride;
Two (9-fluorenyl) zirconium dichlorides of methyl (octyl group) silyl;
Two (2,7-di-t-butyl fluorenyl)-ethyl-1,2-bis-base zirconium dichlorides (IV);
Two-[1-(N, N-diisopropylaminoethyl) boron benzene] hydrogenation trifluoromethane sulfonic acid zirconium;
Methyl-3-butenyl methylene radical (η 5-cyclopentadienyl) (η 5-9-fluorenyl) zirconium dichloride;
Methyl-3-butenyl methylene radical (η 5-cyclopentadienyl) (η 5-2,7-bis--tertiary butyl-9-fluorenyl) zirconium dichloride;
Methyl-4-pentenyl methylene radical (η 5-cyclopentadienyl) (η 5-9-fluorenyl) zirconium dichloride;
Methyl-4-pentenyl methylene radical (η 5-cyclopentadienyl) (η 5-2,7-bis--tertiary butyl-9-fluorenyl) zirconium dichloride;
Phenyl-3-butenyl methylene radical (η 5-cyclopentadienyl) (η 5-9-fluorenyl) zirconium dichloride;
Phenyl-3-butenyl methylene radical (η 5-cyclopentadienyl) (η 5-2,7-bis--tertiary butyl-9-fluorenyl) zirconium dichloride;
Phenyl-4-pentenyl methylene radical (η 5-cyclopentadienyl) (η 5-9-fluorenyl) zirconium dichloride; Or
Phenyl-4-pentenyl methylene radical (η 5-cyclopentadienyl) (η 5-2,7-bis--tertiary butyl-9-fluorenyl) zirconium dichloride.
22. the described method of claim 17, the organoaluminum in wherein said pre-contact organo-aluminium compound is the organo-aluminium compound with following formula:
Al(X 5) n(X 6) 3-n，
(X wherein 5) be the alkyl with 2 to 20 carbon atoms; (X 6) be its any one there is alkoxide or aryl oxide, halogenide or the hydride of 1 to 20 carbon atom; With n be 1 to 3 number, 1 and 3 be also included within.
23. the described method of claim 17, the organoaluminum in wherein said pre-contact organo-aluminium compound is triethyl aluminum (TEA), tri-propyl aluminum, diethyl aluminum ethylate, tri-butyl aluminum, diisobutylaluminium hydride, triisobutyl aluminium, diethylaluminum chloride or their combination.
24. the described method of claim 17 also comprises and makes described pre-contact mixture and described acidic activator-carrier and at least one have the rear organo-aluminium compound that contacts of following formula:
Al(X 5) n(X 6) 3-n，
(X wherein 5) be the alkyl with 1 to 20 carbon atom, (X 6) be any one alkoxide or aryl oxide, halogenide or hydride with 1 to 20 carbon atom; With n be 1 to 3 number, 1 and 3 be also included within, the contact second segment time, with formation, comprise at least one rear contact metallocene, at least one rear rear contact mixture that contacts organo-aluminium compound, contacts alkene or alkynes and fluorinated silica-aluminum oxide after at least one.
25. the described method of claim 17, the alkene in wherein said pre-contact alkene or alkynes or alkynes comprise that per molecule has 2 to 30 carbon atoms and has the compound of at least one carbon-to-carbon double bond or at least one carbon-to-carbon triple bond.
26. the described method of claim 17, the weight that wherein said fluorinated silica-aluminum oxide comprises the described fluorinated silica-aluminum oxide before calcining afterwards based on drying is 5% to 95% aluminum oxide and 2% to 50% fluoride ion by weight by weight.
27. the described method of claim 17, the silica-alumina in wherein said fluorinated silica-aluminum oxide is that pore volume is more than 0.5cc/g and surface-area is 100m 2the silica-alumina that/g is above.
28. the described method of claim 17, metallocene in wherein said pre-contact metallocene is two (indenyl) zirconium dichlorides, two (cyclopentadienyl) zirconium dichloride or two (2,7-di-t-butyl fluorenyl)-ethyl-1,2-bis-base zirconium dichlorides (IV); Described pre-contact organo-aluminium compound comprises triethyl aluminum; Described pre-contact alkene comprises the 1-hexene; And described rear contact acidic activator-carrier is fluorinated silica-aluminum oxide.
29. the described method of claim 17, the organoaluminum in wherein said pre-contact organo-aluminium compound is aluminium pentamethylene, aluminium cyclopentadiene, aluminium cyclopentenes or their arbitrary combination.
30. catalyst composition comprises: at least one contacts metallocene in advance; At least one pre-contact alkene or alkynes; Rear contact acidic activator-carrier; With at least one aluminium pentamethylene; Wherein said acidic activator-carrier is fluorinated silica-aluminum oxide;
The first paragraph time that the contacting of wherein said at least one metallocene and at least one alkene or alkynes continues 1 minute to 9 days is to form pre-contact mixture; With
Described pre-contact mixture and the described fluorinated silica-aluminum oxide second segment time of lasting 1 minute to 24 hours that contacts is to form rear contact mixture; With
Wherein said at least one aluminium pentamethylene forms after pre-contact metallocene compound, organo-aluminium compound and alkene.
31. catalyst composition comprises: at least one contacts metallocene in advance; At least one pre-contact alkene or alkynes; Rear contact acidic activator-carrier; Metal ring pentane with at least one metallocene; Wherein said acidic activator-carrier is fluorinated silica-aluminum oxide;
The first paragraph time that the contacting of wherein said at least one metallocene and at least one alkene or alkynes continues 1 minute to 9 days is to form pre-contact mixture; With
Described pre-contact mixture and the described fluorinated silica-aluminum oxide second segment time of lasting 1 minute to 24 hours that contacts is to form rear contact mixture; With
Wherein said at least one aluminium pentamethylene forms after pre-contact metallocene compound, organo-aluminium compound and alkene.
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